DE102016009846A1 - Fluoroalkylhydrido and fluoroalkylcyanohydridoborates - Google Patents

Abstract

The invention relates to compounds of the formula (I) with fluoroalkylhydridoborate or fluoroalkylcyanohydridoborate anions, as described below, their preparation and use for industrial applications of ionic liquids, in particular as constituent of electrolytes for electrochemical or optoelectronic devices.

Description

The invention relates to compounds of the formula (I) with fluoroalkylhydridoborate or fluoroalkylcyanohydridoborate anions, as described below, their preparation and use for industrial applications of ionic liquids, in particular as constituent of electrolytes for electrochemical or optoelectronic devices.

Ionic liquids or liquid salts are ionic species consisting of an organic cation and a generally inorganic anion. They usually have melting points less than 373 K.

The properties of ionic liquids, eg. As melting point, thermal and electrochemical stability, viscosity, are strongly influenced by the nature of the anion. In contrast, the polarity and hydrophilicity or lipophilicity can be varied by the appropriate choice of the cation / anion pair. Therefore, there is a fundamental need for new ionic liquids, especially with new anions, with varied properties that allow additional possibilities for their use. Most ionic liquids are onium salts. The inorganic salts with these new anions are generally ideal starting materials for the synthesis of onium salts or show interesting properties even in technical fields, such as the field of catalysis, the field of conductive salts or as reagents.

Salts with borate anions are known from many publications.

Tetracyanoborate salts, monofluorotricyanoborates and difluorodicyanoborates with organic cations are described, for example, in US Pat WO 2004/072089 described and are interesting for a variety of applications, especially as an electrolyte component for dye solar cells. The accessibility of the corresponding alkali metal salts as starting materials for the synthesis of these organic salts is essential for a wide industrial application.

Monohydridotricyanoborates are off WO 2012/163489 known. Dihydridodicyanoborates are off WO 2012/163490 and WO 2012/163488 known.

Perfluoroalkyl trifluoroborates are for example WO 2005/105815 known. Alkyl tricyanoborates are for example WO 2013/010641 known. Perfluoroalkylfluorocyanoborates are for example WO 2006/045405 and WO 2011/085966 known.

Onium salts with tetrahydridoborate anions are solid compounds at room temperature and much more unstable than corresponding tetrafluoroborates. Appropriate investigations are in M. Bürchner et al, Chem. Eur. J. 18 (2012), 2254-2262 described.

Attempts to prepare the compound sodium trifluoromethyltrihydridoborate by reacting sodium borohydride with (CH ₃ ) ₃ SiCF ₃ failed as in AA Tyutyunov et al, Fluorine notes, 1 (74), 2011 described.

There continues to be a need for new compounds, in particular as components in electrolyte formulations for electrochemical or optoelectronic devices or as reducing agents in organic synthesis, which should be hydrophobic, less viscous, thermally stable, hydrolysis-stable and electrochemically stable.

Accordingly, it is an object of the present invention to provide alternative compounds which, for example with suitable organic cations, exhibit the property of ionic liquids and are therefore suitable in particular as electrolyte components for electrochemical or optoelectronic devices, or which are used, for example, with inorganic cations as catalysts or reducing agents in organic synthesis , as conductive salts or for the synthesis of ionic liquids.

The present object is achieved by the compounds according to the invention, the process for their preparation and their use.

Surprisingly, it has been found that the compounds of the formula (I) according to the invention, as described below, have a high electrochemical stability against anodic oxidation and are hydrophobic and hydrolysis stable at the same time. They show, in particular over Cyanohydridoboraten a higher electrochemical stability against anodic oxidation.

A first subject of the invention are thus compounds of the formula (I) Cat [(C _n F _{(2n + 1) -m} H _m ) BH _x (CN) _3-x ] (I) in which
n is an integer from 1 to 12,
m is 0, 1, 2, 3 or 4,
x is 1, 2 or 3 and
Cat means an organic or inorganic cation.

A fluoroalkyl group C _n F _{(2n + 1) -m} H _m having 1 to 12 C atoms corresponds to a straight-chain or branched alkyl group having 1 to 12 C atoms, wherein 1, 2, 3 or 4 H atoms by F atoms are replaced. A preferred fluoroalkyl group is 2,2,2-trifluoroethyl.

A perfluoroalkyl group having 1 to 12 C atoms [C _n F _{(2n + 1) -m} H _m and m = 0] corresponds to a straight-chain or branched alkyl group having 1 to 12 C atoms, where all H atoms are represented by F atoms are replaced. Alkyl groups having 1 to 12 C atoms are, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, pentyl, 1-, 2- or 3-methylbutyl, 1,1-, 1,2 or 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl. Unless the alkyl group is unspecified, it is a linear alkyl group.

Preferred groups C _n F _{(2n + 1) -m} H _m are each independently of one another straight-chain or branched perfluoroalkyl groups having 1 to 6 C atoms or 2,2,2-trifluoroethyl.

N is preferably 2, 3 or 4. n is particularly preferably 2, 3 or 4 and m is 0 or 2.

Most preferably C _n F _{(2n + 1) -m} H _{m is} pentafluoroethyl or nonafluorobutyl.

Another object of the invention are therefore compounds of formula (I), as described above, wherein the variable n is 2, 3 or 4.

Preferred anions of the compounds of the formula (I) according to the invention are, for example
Pentafluorethyltrihydridoborat,
Heptafluorpropyltrihydridoborat,
Nonafluorbutyltrihydridoborat,
Pentafluorethyldihydridocyanoborat,
Heptafluorpropyldihydridocyanoborat,
Nonafluorbutyldihydridocyanoborat,
Pentafluorethylhydridodicyanoborat,
Heptafluorpropylhydridodicyanoborat,
Nonafluorbutylhydridodicyanoborat.

The compounds according to the invention show similar hydrolytic stability to the known hydridotricyanoborates or dihydridodicyanoborates, but at the same time have higher hydrophobicity and electrochemical stability.

Preferably, the organic cations of the compounds of formula (I) wherein x is 1 or 2 are organic cations selected from the group consisting of ammonium, sulfonium, oxonium, phosphonium, iodonium, tritylium, Uronium, thiouronium, guanidinium cations or heterocyclic cations. Examples of organic cations are also polyammonium ions with a degree of charge 4. Preferred organic cations for compounds of formula (I) wherein x is 1 or 2 are represented by formulas (1) to (10) with the following definitions.

• – H
• – OR¹, mit der Bedingung, dass jeweils nur ein Substituent R⁰ OR¹ bedeuten kann, oder
• – N(R¹)₂, mit der Bedingung, dass jeweils nur ein Substituent R⁰ N(R¹)₂ bedeuten kann, oder
• – geradkettiges oder verzweigtes Alkyl mit 1-20 C-Atomen,
• – geradkettiges oder verzweigtes Alkenyl mit 2-20 C-Atomen und einer oder mehreren Doppelbindungen,
• – geradkettiges oder verzweigtes Alkinyl mit 2-20 C-Atomen und einer oder mehreren Dreifachbindungen,
• – gesättigtes oder teilweise ungesättigtes Cycloalkyl mit 3-7 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,
• – Aryl mit 6 bis 12 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,

bedeutet,
wobei ein oder zwei Substituenten R⁰ vollständig mit Halogen substituiert sein kann/können oder ein oder mehrere Substituenten R⁰ teilweise mit Halogen, -OR¹, -CN, -N(R¹)₂, -C(O)OR¹, -OC(O)R¹, -OC(O)OR¹, -C(O)R¹, -C(O)N(R¹)₂, -SO₂N(R¹)₂, -C(O)X, -SO₃R¹, -SO₂X, -NO₂, -SR¹, -S(O)R¹ und/oder -SO₂R¹ substituiert sein kann/können,
und wobei ein oder zwei nicht benachbarte und nicht α-ständige Kohlenstoffatome des Restes R⁰ jeweils unabhängig durch Atome und/oder Atomgruppierungen ausgewählt aus der Gruppe -O-, -S-, -S(O)-, -SO₂-, -SO₂O-, -C(O)-, -C(O)O-, -N⁺(R¹)₂-, -P(O)R¹O-, -C(O)NR¹-, -SO₂NR¹-, OP(O)R¹O-, -P(O)(N(R¹)₂)NR¹-, -P(R¹)₂=N- oder -P(O)R¹- ersetzt sein können, worin R¹ jeweils unabhängig voneinander für H; nicht oder teilweise fluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht und X jeweils unabhängig voneinander für Halogen steht.Preferred ammonium cations are described by the formula (1) [N (R ⁰ ) ₄ ] ⁺ (1), in which
R ⁰ each independently

• - H
• - OR ¹ , with the proviso that in each case only one substituent R ⁰ can mean OR ¹ , or
• - N (R ¹ ) ₂ , with the proviso that in each case only one substituent R ^{0 can} denote N (R ¹ ) ₂ , or
• Straight-chain or branched alkyl having 1-20 C atoms,
• Straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
• Straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
• Saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
• - aryl having 6 to 12 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,

means
where one or two substituents R ^{0 can be} completely substituted by halogen or one or more substituents R ^{0 are} partially substituted by halogen, -OR ¹ , -CN, -N (R ¹ ) ₂ , -C (O) OR ¹ , - OC (O) R ¹ , -OC (O) OR ¹ , -C (O) R ¹ , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -C (O) X, -SO ₃ R ¹ , -SO ₂ X, -NO ₂ , -SR ¹ , -S (O) R ¹ and / or -SO ₂ R ¹ may be substituted,
and wherein one or two non-adjacent and non-α-carbon atoms of the radical R ^{0 are} each independently represented by atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, - SO ₂ O-, -C (O) -, -C (O) O-, -N ⁺ (R ¹ ) ₂ -, -P (O) R ¹ O-, -C (O) NR ¹ -, - SO ₂ NR ¹ -, OP (O) R ¹ O-, -P (O) (N (R ¹ ) ₂ ) NR ¹ -, -P (R ¹ ) ₂ = N- or -P (O) R ¹ - may be replaced, wherein R ^{1 are} each independently H; non-or partially fluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl and each X is independently halogen.

• – geradkettiges oder verzweigtes Alkyl mit 1-8 C-Atomen,
• – nicht substituiertes Aryl mit 6 bis 30 C-Atomen oder durch R^1*, OR¹, SR¹, N(R¹)₂, CN oder Halogen substituiertes Aryl mit 6 bis 30 C-Atomen bedeutet, wobei im Fall der Sulfoniumkationen der Formel (2) die Substituenten R⁰¹ jeweils unabhängig voneinander auch (R''')₂N bedeuten können,

wobei R¹ jeweils unabhängig voneinander für H; nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht, R^1* jeweils unabhängig voneinander für nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₆-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht und R''' jeweils unabhängig voneinander für geradkettiges oder verzweigtes Alkyl mit 1 bis 6 C-Atomen steht.Preferred sulfonium cations are represented by the formula (2), and preferred oxonium cations are represented by the formula (3). [S (R ⁰¹ ) ₃ ] ⁺ (2) or [O (R ⁰¹ ) ₃ ] ⁺ (3), in which
R ⁰¹ each independently

• Straight-chain or branched alkyl having 1-8 C atoms,
• - Unsubstituted aryl having 6 to 30 carbon atoms or by R ^{1 *} , OR ¹ , SR ¹ , N (R ¹ ) ₂ , CN or halogen-substituted aryl having 6 to 30 carbon atoms, wherein in the case of Sulfoniumkationen the Formula (2) the substituents R ^{01 can} each independently also be (R ''') ₂ N,

wherein R ^{1 are} each independently H; not or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl, R ^{1 *} each independently of one another are not or partially or perfluorinated straight-chain or branched C ₁ - to C ₆ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl and R '''each independently represents straight-chain or branched alkyl having 1 to 6 C atoms.

• – N(R^1**)₂
• – O(R^1**), oder
• – geradkettiges oder verzweigtes Alkyl mit 1-20 C-Atomen,
• – geradkettiges oder verzweigtes Alkenyl mit 2-20 C-Atomen und einer oder mehreren Doppelbindungen,
• – geradkettiges oder verzweigtes Alkinyl mit 2-20 C-Atomen und einer oder mehreren Dreifachbindungen,
• – gesättigtes oder teilweise ungesättigtes Cycloalkyl mit 3-7 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,
• – Aryl mit 6 bis 12 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann

bedeutet,
wobei ein oder zwei Substituenten R² vollständig mit Halogen substituiert sein kann/können oder ein oder mehrere Substituenten R² teilweise mit Halogen, -OR¹, -CN, -N(R¹)₂, -C(O)OR¹, -OC(O)R¹, -OC(O)OR¹, -C(O)R¹, -C(O)N(R¹)₂, -SO₂N(R¹)₂, -C(O)X, -SO₃R¹, -SO₂X, -NO₂, -SR¹, -S(O)R¹ und/oder -SO₂R¹ substituiert sein kann/können,
und wobei ein oder zwei nicht benachbarte und nicht α-ständige Kohlenstoffatome des Restes R² jeweils unabhängig durch Atome und/oder Atomgruppierungen ausgewählt aus der Gruppe -O-, -S-, -S(O)-, -SO₂-, -SO₂O-, -C(O)-, -C(O)O-, -N⁺(R¹)₂-, -P(O)R¹O-, -C(O)NR¹-, -SO₂NR¹-, -OP(O)R¹O-, -P(O)(N(R¹)₂)NR¹-, -P(R¹)₂=N- oder -P(O)R¹- ersetzt sein können, worin R¹ jeweils unabhängig voneinander für H; nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht und X jeweils unabhängig voneinander für Halogen steht und R^1** jeweils unabhängig voneinander für nicht oder teilweise fluoriertes geradkettiges oder verzweigtes C₁- bis C₆-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht.Preferred phosphonium cations are described by the formula (4) [P (R ² ) ₄ ] ⁺ (4), in which
R ² each independently

• - N (R ^{1 **} ) ₂
• - O (R ^{1 **} ), or
• Straight-chain or branched alkyl having 1-20 C atoms,
• Straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
• Straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
• Saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
• - Aryl having 6 to 12 carbon atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms

means
where one or two substituents R ^{2 may be} completely halogen-substituted or one or more substituents R ^{2 may be} partially substituted by halogen, -OR ¹ , -CN, -N (R ¹ ) ₂ , -C (O) OR ¹ , - OC (O) R ¹ , -OC (O) OR ¹ , -C (O) R ¹ , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -C (O) X, -SO ₃ R ¹ , -SO ₂ X, -NO ₂ , -SR ¹ , -S (O) R ¹ and / or -SO ₂ R ¹ may be substituted,
and wherein one or two non-adjacent and non-α-carbon atoms of the radical R ^{2 are} each independently substituted by atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, - SO ₂ O-, -C (O) -, -C (O) O-, -N ⁺ (R ¹ ) ₂ -, -P (O) R ¹ O-, -C (O) NR ¹ -, - SO ₂ NR ¹ -, -OP (O) R ¹ O-, -P (O) (N (R ¹ ) ₂ ) NR ¹ -, -P (R ¹ ) ₂ = N- or -P (O) R ¹ - may be replaced, wherein R ^{1 are} each independently H; not or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; each unsubstituted or substituted phenyl, and each X is independently halogen and R ^{1 ** are} each independently of one another unsubstituted or partially fluorinated straight or branched C ₁ to C ₆ alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl.

wobei
die Arylgruppe Ar jeweils unabhängig voneinander Aryl mit 6 bis 30 C-Atomen bedeutet, die unsubstituiert oder jeweils unabhängig voneinander durch mindestens eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 20 C-Atomen, durch mindestens eine geradkettige oder verzweigte Alkenylgruppe mit 2 bis 20 C-Atomen und einer oder mehrerer Doppelbindungen, durch mindestens eine geradkettige oder verzweigte Alkinylgruppe mit 2 bis 20 C-Atomen und einer oder mehrerer Doppelbindungen, durch R^1*, durch NO₂, durch SR¹, durch OR¹, durch N(R¹)₂, durch CN und/oder durch Halogen substituiert sein kann und worin
R¹ jeweils unabhängig voneinander für H; nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht und R^1* jeweils unabhängig voneinander für nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₆-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht.Preferred iodonium cations are described by the formula (5)

in which
each aryl group Ar is independently aryl having 6 to 30 carbon atoms which is unsubstituted or independently of one another by at least one straight-chain or branched alkyl group having 1 to 20 carbon atoms, by at least one straight-chain or branched alkenyl group having 2 to 20 carbon atoms. Atoms and one or more double bonds, by at least one straight-chain or branched alkynyl group having 2 to 20 C atoms and one or more double bonds, by R ^{1 *} , by NO ₂ , by SR ¹ , by OR ¹ , by N (R ¹ ) ₂ , may be substituted by CN and / or by halogen and wherein
Each R ¹ is independently H; not or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl and R ^{1 * are} each independently of one another not or partially or perfluorinated straight-chain or branched C ₁ - to C ₆ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl.

wobei
die Phenylgruppen Ph unsubstituiert oder jeweils unabhängig voneinander durch mindestens eine geradkettige oder verzweigte Alkylgruppen mit 1 bis 20 C-Atomen, durch mindestens eine geradkettige oder verzweigte Alkenylgruppen mit 2 bis 20 C-Atomen und einer oder mehrerer Doppelbindungen, durch mindestens eine geradkettige oder verzweigte Alkinylgruppe mit 2 bis 20 C-Atomen und einer oder mehrerer Doppelbindungen, durch OR¹, durch SR¹, durch N(R¹)₂, durch CN und/oder durch Halogen substituiert sein kann und worin
R¹ jeweils unabhängig voneinander für H; nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht.Preferred tritylium cations are described by the formula (6)

in which
the phenyl groups Ph are unsubstituted or in each case independently of one another by at least one straight-chain or branched alkyl groups having 1 to 20 C atoms, by at least one straight-chain or branched alkenyl groups having 2 to 20 C atoms and one or more double bonds, by at least one straight-chain or branched alkynyl group may be substituted by 2 to 20 carbon atoms and one or more double bonds, by OR ¹ , by SR ¹ , by N (R ¹ ) ₂ , by CN and / or by halogen and wherein
Each R ¹ is independently H; not or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl.

• – H oder N(R^1*)₂ oder
• – geradkettiges oder verzweigtes Alkyl mit 1 bis 20 C-Atomen,
• – geradkettiges oder verzweigtes Alkenyl mit 2-20 C-Atomen und einer oder mehreren Doppelbindungen,
• – geradkettiges oder verzweigtes Alkinyl mit 2-20 C-Atomen und einer oder mehreren Dreifachbindungen,
• – gesättigtes oder teilweise ungesättigtes Cycloalkyl mit 3-7 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,
• – Aryl mit 6 bis 12 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,

bedeuten,
wobei ein Substituent oder zwei Substituenten der Substituenten R³ bis R⁷ vollständig mit Halogen substituiert sein kann/können oder ein oder mehrere Substituenten R³, R⁴, R⁶ und R⁷ teilweise mit Halogen, -OR¹, -CN, -N(R¹)₂, -C(O)OR¹, -OC(O)R¹, -OC(O)OR¹, -C(O)R¹, -C(O)N(R¹)₂, -SO₂N(R¹)₂, -C(O)X, -SO₃R¹, -SO₂X, -NO₂, -SR¹, -S(O)R¹ und/oder -SO₂R¹ substituiert sein kann/können,
und wobei ein oder zwei nicht benachbarte und nicht α-ständige Kohlenstoffatome der Reste R³ bis R⁷ jeweils unabhängig durch Atome und/oder Atomgruppierungen ausgewählt aus der Gruppe -O-, -S-, -S(O)-, -SO₂-, -SO₂O-, -C(O)-, -C(O)O-, -N⁺(R¹)₂-, -P(O)R¹O-, -C(O)NR¹-, -SO₂NR¹-, -OP(O)R¹O-, -P(O)(N(R¹)₂)NR¹-, -P(R¹)₂=N- oder -P(O)R¹- ersetzt sein können, worin R¹ jeweils unabhängig voneinander für H; nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht, R^1* jeweils unabhängig voneinander für nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht und X jeweils unabhängig voneinander für Halogen steht.Preferred uronium cations are represented by the formula (7), and preferred thiouronium cations are represented by the formula (8). [C (NR ³ R ⁴ ) (OR ⁵ ) (NR ⁶ R ⁷ )] ⁺ (7) or [C (NR ³ R ⁴ ) (SR ⁵ ) (NR ⁶ R ⁷ )] ⁺ (8), in which
R ³ to R ^{7 are} each independently

• - H or N (R ^{1 *} ) ₂ or
• Straight-chain or branched alkyl having 1 to 20 C atoms,
• Straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
• Straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
• Saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
• - aryl having 6 to 12 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,

mean,
wherein a substituent or two substituents of the substituents R ³ to R ^{7 may be} completely halogen-substituted or one or more substituents R ³ , R ⁴ , R ⁶ and R ^{7 are} partially halogen, -OR ¹ , -CN, -N (R ¹ ) ₂ , -C (O) OR ¹ , -OC (O) R ¹ , -OC (O) OR ¹ , -C (O) R ¹ , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -C (O) X, -SO ₃ R ¹ , -SO ₂ X, -NO ₂ , -SR ¹ , -S (O) R ¹ and / or -SO ₂ R ¹ can be substituted,
and wherein one or two non-adjacent and non-α-carbon atoms of R ³ to R ^{7 are} each independently selected from atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -SO ₂ O-, -C (O) -, -C (O) O-, -N ⁺ (R ¹ ) ₂ -, -P (O) R ¹ O-, -C (O) NR ¹ -, -SO ₂ NR ¹ -, -OP (O) R ¹ O-, -P (O) (N (R ¹ ) ₂ ) NR ¹ -, -P (R ¹ ) ₂ = N- or -P ( O) R ¹ - may be replaced, wherein R ^{1 are} each independently H; not or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl, each R ^{1 *} is independently or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl and each X is independently halogen.

• – H, CN, OR^1* oder N(R^1*)₂,
• – geradkettiges oder verzweigtes Alkyl mit 1 bis 20 C-Atomen,
• – geradkettiges oder verzweigtes Alkenyl mit 2-20 C-Atomen und einer oder mehreren Doppelbindungen,
• – geradkettiges oder verzweigtes Alkinyl mit 2-20 C-Atomen und einer oder mehreren Dreifachbindungen,
• – gesättigtes oder teilweise ungesättigtes Cycloalkyl mit 3-7 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,
• – Aryl mit 6 bis 12 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,

bedeuten,
wobei ein Substituent oder zwei Substituenten der Substituenten R⁸ bis R¹³ vollständig mit Halogen substituiert sein kann/können oder ein oder mehrere Substituenten R⁸ bis R¹³ teilweise mit Halogen, -OR¹, -CN, -N(R¹)₂, -C(O)OR¹, -OC(O)R¹, -OC(O)OR¹, -C(O)R¹, -C(O)N(R¹)₂, -SO₂N(R¹)₂, -C(O)X, -SO₃R¹, -SO₂X, -NO₂, -SR¹, -S(O)R¹ und/oder -SO₂R¹ substituiert sein kann/können,
und wobei ein oder zwei nicht benachbarte und nicht α-ständige Kohlenstoffatome der Reste R⁸ bis R¹³ jeweils unabhängig durch Atome und/oder Atomgruppierungen ausgewählt aus der Gruppe -O-, -S-, -S(O)-, -SO₂-, -SO₂O-, -C(O)-, -C(O)O-, -N⁺(R¹)₂-, -P(O)R¹O-, -C(O)NR¹-, -SO₂NR¹-, -OP(O)R¹O-, -P(O)(N(R¹)₂)NR¹-, -P(R¹)₂=N- oder -P(O)R¹- ersetzt sein können, worin R¹ jeweils unabhängig voneinander für H; nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht, X jeweils unabhängig voneinander für Halogen steht und R^1* für nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht.Preferred guanidinium cations are described by the formula (9) [C (NR ⁸ R ⁹ ) (NR ¹⁰ R ¹¹ ) (NR ¹² R ¹³ )] ⁺ (9) in which
R ⁸ to R ^{13 are} each independently

• H, CN, OR ^{1 *} or N (R ^{1 *} ) ₂ ,
• Straight-chain or branched alkyl having 1 to 20 C atoms,
• Straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
• Straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
• Saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
• - aryl having 6 to 12 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,

mean,
where one substituent or two substituents of the substituents R ⁸ to R ^{13 can be} completely substituted by halogen or one or more substituents R ⁸ to R ^{13 are} partially substituted by halogen, -OR ¹ , -CN, -N (R ¹ ) ₂ , -C (O) OR ¹ , -OC (O) R ¹ , -OC (O) OR ¹ , -C (O) R ¹ , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -C (O) X, -SO ₃ R ¹ , -SO ₂ X, -NO ₂ , -SR ¹ , -S (O) R ¹ and / or -SO ₂ R ¹ may be substituted / can .
and wherein one or two non-adjacent and non-α-carbon atoms of R ⁸ to R ^{13 are} each independently selected from atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -SO ₂ O-, -C (O) -, -C (O) O-, -N ⁺ (R ¹ ) ₂ -, -P (O) R ¹ O-, -C (O) NR ¹ -, -SO ₂ NR ¹ -, -OP (O) R ¹ O-, -P (O) (N (R ¹ ) ₂ ) NR ¹ -, -P (R ¹ ) ₂ = N- or -P ( O) R ¹ - may be replaced, wherein R ^{1 are} each independently H; not or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; each unsubstituted or substituted phenyl, each X is independently halogen and R ^{1 * is} not or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl.

wobei die Substituenten R^1' bis R^4' jeweils unabhängig voneinander

• – H,
• – geradkettiges oder verzweigtes Alkyl mit 1-20 C-Atomen, welche auch fluoriert oder perfluoriert sein können,
• – geradkettiges oder verzweigtes Alkenyl mit 2-20 C-Atomen und einer oder mehreren Doppelbindungen, welche auch fluoriert oder perfluoriert sein können,
• – geradkettiges oder verzweigtes Alkinyl mit 2-20 C-Atomen und einer oder mehreren Dreifachbindungen, welche auch fluoriert sein können,
• – gesättigtes oder teilweise ungesättigtes Cycloalkyl mit 3-7 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,
• – Aryl mit 6 bis 12 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,
• – gesättigtes, teilweise oder vollständig ungesättigtes Heteroaryl, Heteroaryl-C₁-C₆-alkyl oder Aryl-C₁-C₆-alkyl,

bedeuten,
wobei der Substituent R^2' jeweils unabhängig voneinander noch die Bedeutung F, Cl, Br, I, -CN, OR¹, -N(R¹)₂, -P(O)(R¹)₂, -P(O)(OR¹)₂, -P(O)(N(R¹)₂)₂, -C(O)R¹, -C(O)OR¹, -C(O)X, -C(O)N(R¹)₂, -SO₂N(R¹)₂, -SO₃R¹, -SO₂X, -SR¹, -S(O)R¹, -SO₂R¹ und/oder NO₂ haben kann, unter der Bedingung, dass die Substituenten R^1', R^3' und R^4' in diesem Fall unabhängig voneinander H und/oder geradkettiges oder verzweigtes Alkyl mit 1 bis 20 C-Atomen und/oder geradkettiges oder verzweigtes Alkenyl mit 2 bis 20 C-Atomen bedeuten,
wobei die Substituenten R^1', R^2', R^3' und/oder R^4' zusammen ein Ringsystem bilden können,
wobei ein, zwei oder drei Substituenten R^1' bis R^4', aber nicht gleichzeitig R^1' und R^4', vollständig mit Halogen substituiert sein können oder ein oder mehrere der Substituenten R^1' bis R^4' teilweise mit Halogen, -OR¹, -CN, -N(R¹)₂, -C(O)OR¹, -OC(O)R¹, -OC(O)OR¹, -C(O)R¹, -C(O)N(R¹)₂, -SO₂N(R¹)₂, -C(O)X, -SO₃H, -SO₂X, -NO₂, -SR¹, -S(O)R1 und/oder -SO₂R¹ substituiert sein können,
und wobei ein oder zwei nicht benachbarte und nicht α-ständige Kohlenstoffatome der Reste R^1' bis R^4' jeweils unabhängig durch Atome und/oder Atomgruppierungen ausgewählt aus der Gruppe -O-, -S-, -S(O)-, -SO₂-, -SO₂O-, -C(O)-, -C(O)O-, -N⁺(R¹)₂-, -P(O)R¹O-, -C(O)NR¹-, -SO₂NR¹-, -OP(O)R¹O-, -P(O)(N(R¹)₂)NR¹-, -P(R¹)₂=N- oder -P(O)R¹- ersetzt sein können, worin R¹ jeweils unabhängig voneinander für H; nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht und X jeweils unabhängig voneinander für Halogen steht.Preferred heterocyclic cations are described by the formula (10) [HetN] ⁺ (10), wherein [HetN] ^{+ is} a heterocyclic cation selected from the group comprising

wherein the substituents R ^{1 '} to R ^{4' are} each independently

• - H,
• Straight-chain or branched alkyl having 1-20 C atoms, which may also be fluorinated or perfluorinated,
• Straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, which may also be fluorinated or perfluorinated,
• Straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, which may also be fluorinated,
• Saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
• - aryl having 6 to 12 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
• Saturated, partially or completely unsaturated heteroaryl, heteroaryl-C ₁ -C ₆ -alkyl or aryl-C ₁ -C ₆ -alkyl,

mean,
where the substituent R ^{2 'is} each independently of one another the meaning F, Cl, Br, I, -CN, OR ¹ , -N (R ¹ ) ₂ , -P (O) (R ¹ ) ₂ , -P (O) (OR ¹ ) ₂ , -P (O) (N (R ¹ ) ₂ ) ₂ , -C (O) R ¹ , -C (O) OR ¹ , -C (O) X, -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -SO ₃ R ¹ , -SO ₂ X, -SR ¹ , -S (O) R ¹ , -SO ₂ R ¹ and / or NO ₂ have can, under the condition that the substituents R ^{1 '} , R ^3' and R ^{4 '} in this case independently H and / or straight-chain or branched alkyl having 1 to 20 carbon atoms and / or straight-chain or branched alkenyl with 2 to 20 C atoms mean
where the substituents R ^{1 '} , R ^2' , R ^{3 '} and / or R ^4' together can form a ring system,
where one, two or three substituents R ^{1 '} to R ^4' , but not simultaneously R ^{1 '} and R ^4' , may be completely substituted by halogen or one or more of the substituents R ^{1 '} to R ^{4' are} partially substituted by halogen, OR ¹ , -CN, -N (R ¹ ) ₂ , -C (O) OR ¹ , -OC (O) R ¹ , -OC (O) OR ¹ , -C (O) R ¹ , -C (O ) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -C (O) X, -SO ₃ H, -SO ₂ X, -NO ₂ , -SR ¹ , -S (O) R ¹ and / or -SO ₂ R ¹ may be substituted,
and wherein one or two non-adjacent and non-α-carbon atoms of the radicals R ^{1 '} to R ^{4' are} each independently substituted by atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, - SO ₂ -, -SO ₂ O-, -C (O) -, -C (O) O-, -N ⁺ (R ¹ ) ₂ -, -P (O) R ¹ O-, -C (O) NR ¹ -, -SO ₂ NR ¹ -, -OP (O) R ¹ O-, -P (O) (N (R ¹ ) ₂ ) NR ¹ -, -P (R ¹ ) ₂ = N- or - P (O) R ¹ - may be replaced, wherein R ^{1 are} each independently H; not or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl and each X is independently halogen.

Halogen is F, Cl, Br or I, preferably F, Cl or Br, most preferably F or Cl.

• – OR^1* bedeutet, mit der Bedingung, dass jeweils nur ein Substituent R⁰ OR^1* bedeuten kann, oder
• – N(R^1*)₂ bedeutet, mit der Bedingung, dass jeweils nur ein Substituent R⁰ N(R^1*)₂ bedeuten kann, oder
• – geradkettiges oder verzweigtes Alkyl mit 1-20 C-Atomen,
• – geradkettiges oder verzweigtes Alkenyl mit 2-20 C-Atomen und einer oder mehreren Doppelbindungen,
• – geradkettiges oder verzweigtes Alkinyl mit 2-20 C-Atomen und einer oder mehreren Dreifachbindungen,
• – gesättigtes oder teilweise ungesättigtes Cycloalkyl mit 3-7 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,
• – Aryl mit 6 bis 12 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,

bedeutet,
wobei ein oder zwei Substituenten R⁰ vollständig mit Halogen substituiert sein kann/können oder ein oder mehrere Substituenten R⁰ teilweise mit Halogen, -OR^1*, -CN, -N(R¹)₂, -C(O)OR^1*, -OC(O)R^1*, -OC(O)OR^1*, -C(O)R^1*, -C(O)N(R¹)₂, -SO₂N(R¹)₂, -SO₂X, -SR^1*, -S(O)R^1* und/oder -SO₂R^1* substituiert sein kann/können, und wobei ein oder zwei nicht benachbarte und nicht α-ständige Kohlenstoffatome des Restes R⁰ jeweils unabhängig durch Atome und/oder Atomgruppierungen ausgewählt aus der Gruppe -O-, -S-, -S(O)-, -SO₂-, -SO₂O-, -C(O)-, -C(O)O-, -N⁺(R^1*)₂-, -P(O)R^1*O-, -C(O)NR^1*-, -SO₂NR^{1 *}-, -OP(O)R^1*O-, -P(O)(N(R¹)₂)NR^1*-, -P(R^1*)₂=N- oder -P(O)R^1*- ersetzt sein können,
wobei
R¹ jeweils unabhängig voneinander für H nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht,
R^1* jeweils unabhängig voneinander für nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht und X jeweils unabhängig voneinander für Halogen steht.Preferred organic cations for compounds of the formula (I) in which x is 3 are organic cations of the formulas (1), (4), (7) to (10) with the following definitions:
Preferred ammonium cations for compounds of the formula (I) in which x is 3 are described by the formula (1) [N (R ⁰ ) ₄ ] ⁺ (1), in which
R ⁰ each independently

• - OR ^{1 *} means with the condition that in each case only one substituent R ⁰ can mean OR ^{1 *} , or
• - N (R ^{1 *} ) ₂ , with the condition that only one substituent R ⁰ N (R ^{1 *} ) _{2 may} mean, or
• Straight-chain or branched alkyl having 1-20 C atoms,
• Straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
• Straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
• Saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
• - aryl having 6 to 12 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,

means
where one or two substituents R ^{0 can be} completely halogen-substituted or one or more substituents R ^{0 can be} partially substituted by halogen, -OR ^{1 *} , -CN, -N (R ¹ ) ₂ , -C (O) OR ^{1 *} , -OC (O) R ^{1 *} , -OC (O) OR ^{1 *} , -C (O) R ^{1 *} , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -SO ₂ X, -SR ^{1 *} , -S (O) R ^{1 *} and / or -SO ₂ R ^{1 *} can be substituted, and wherein one or two non-adjacent and non-α-carbon atoms of the radical R ⁰ each independently selected by atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -SO ₂ O-, - C (O) -, -C (O) O-, -N ⁺ (R ^{1 *} ) ₂ -, -P (O) R ^{1 *} O-, -C (O) NR ^{1 *} -, -SO ₂ NR ^{1 *} , -OP (O) R ^{1 *} O-, -P (O) (N (R ¹ ) ₂ ) NR ^{1 *} -, -P (R ^{1 *} ) ₂ = N- or -P (O) R ^{1 *} - can be replaced,
in which
R ^{1 are} each independently of one another not H or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl,
R ^{1 * are} each independently of one another not or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl and each X is independently halogen.

• – N(R^1**)₂
• – O(R^1**), oder
• – geradkettiges oder verzweigtes Alkyl mit 1-20 C-Atomen,
• – geradkettiges oder verzweigtes Alkenyl mit 2-20 C-Atomen und einer oder mehreren Doppelbindungen,
• – geradkettiges oder verzweigtes Alkinyl mit 2-20 C-Atomen und einer oder mehreren Dreifachbindungen,
• – gesättigtes oder teilweise ungesättigtes Cycloalkyl mit 3-7 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,
• – Aryl mit 6 bis 12 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann

bedeutet,
wobei ein oder zwei Substituenten R² vollständig mit Halogen substituiert sein kann/können oder ein oder mehrere Substituenten R² teilweise mit Halogen, -OR^1*, -CN, -N(R¹)₂, -C(O)OR^1*, -OC(O)R^1*, -OC(O)OR^1*, -C(O)R^1*, -C(O)N(R¹)₂, -SO₂N(R¹)₂, -SO₂X, -SR^1*, -S(O)R^1* und/oder -SO₂R^1* substituiert sein kann/können,
und wobei ein oder zwei nicht benachbarte und nicht α-ständige Kohlenstoffatome des Restes R² jeweils unabhängig durch Atome und/oder Atomgruppierungen ausgewählt aus der Gruppe -O-, -S-, -S(O)-, -SO₂-, -SO₂O-, -C(O)-, -C(O)O-, -N⁺(R^1*)₂-, -P(O)R¹O-, -C(O)NR^1*-, -SO₂NR^1*-, -OP(O)R^1*O-, -P(O)(N(R¹)₂)NR^1*-, -P(R^1*)₂=N- oder -P(O)R^1*- ersetzt sein können,
wobei
R¹ jeweils unabhängig voneinander für H nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht,
R^1* jeweils unabhängig voneinander für nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht,
R^1** jeweils unabhängig voneinander für nicht oder teilweise fluoriertes geradkettiges oder verzweigtes C₁- bis C₆-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht und X jeweils unabhängig voneinander für Halogen steht.Preferred phosphonium cations for compounds of the formula (I) in which x is 3 are described by the formula (4), [P (R ² ) ₄ ] ⁺ (4), in which
R ² each independently

• - N (R ^{1 **} ) ₂
• - O (R ^{1 **} ), or
• Straight-chain or branched alkyl having 1-20 C atoms,
• Straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
• Straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
• Saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
• - Aryl having 6 to 12 carbon atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms

means
where one or two substituents R ^{2 can be} completely substituted by halogen or one or more substituents R ^{2 can be} partially substituted by halogen, -OR ^{1 *} , -CN, -N (R ¹ ) ₂ , -C (O) OR ^{1 *} , -OC (O) R ^{1 *} , -OC (O) OR ^{1 *} , -C (O) R ^{1 *} , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -SO ₂ X, -SR ^{1 *} , -S (O) R ^{1 *} and / or -SO ₂ R ^{1 *} may be substituted,
and wherein one or two non-adjacent and non-α-carbon atoms of the radical R ^{2 are} each independently substituted by atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, - SO ₂ O-, -C (O) -, -C (O) O-, -N ⁺ (R ^{1 *} ) ₂ -, -P (O) R ¹ O-, -C (O) NR ^{1 *} - , -SO ₂ NR ^{1 *} -, -OP (O) R ^{1 *} O-, -P (O) (N (R ¹ ) ₂ ) NR ^{1 *} -, -P (R ^{1 *} ) ₂ = N- or -P (O) R ^{1 *} - can be replaced,
in which
R ^{1 are} each independently of one another not H or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl,
R ^{1 * are} each independently of one another not or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl,
R ^{1 ** are} each independently of one another unsubstituted or partially fluorinated straight-chain or branched C ₁ - to C ₆ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl and each X is independently halogen.

• – N(R^1*)₂ bedeuten, oder
• – geradkettiges oder verzweigtes Alkyl mit 1 bis 20 C-Atomen,
• – geradkettiges oder verzweigtes Alkenyl mit 2-20 C-Atomen und einer oder mehreren Doppelbindungen,
• – geradkettiges oder verzweigtes Alkinyl mit 2-20 C-Atomen und einer oder mehreren Dreifachbindungen,
• – gesättigtes oder teilweise ungesättigtes Cycloalkyl mit 3-7 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,
• – Aryl mit 6 bis 12 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,

bedeuten,
wobei ein Substituent oder zwei Substituenten der Substituenten R³ bis R⁷ vollständig mit Halogen substituiert sein kann/können oder ein oder mehrere Substituenten R³, R⁴, R⁶ und R⁷ teilweise mit Halogen, -OR^1*, -CN, -N(R^1*)₂, -C(O)OR^1*, -OC(O)R^1*, -OC(O)OR^1*, -C(O)R^1*, -C(O)N(R¹)₂, -SO₂N(R¹)₂, -SO₂X, -SR^1*, -S(O)R^1* und/oder -SO₂R^1* substituiert sein kann/können,
und wobei ein oder zwei nicht benachbarte und nicht α-ständige Kohlenstoffatome der Reste R³ bis R⁷ jeweils unabhängig durch Atome und/oder Atomgruppierungen ausgewählt aus der Gruppe -O-, -S-, -S(O)-, -SO₂-, -SO₂O-, -C(O)-, -C(O)O-, -N⁺(R^1*)₂-, -P(O)R^1*O-, -C(O)NR^1*-, -SO₂NR^1*-, -OP(O)R^1*O-, -P(O)(N(R¹)₂)NR^1*-, -P(R^1*)₂=N- oder -P(O)R^1*- ersetzt sein können,
wobei
R¹ jeweils unabhängig voneinander für H nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht,
R^1* jeweils unabhängig voneinander für nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht und X jeweils unabhängig voneinander für Halogen steht.Preferred uronium cations or thiouronium cations for compounds of the formula (I) in which x is 3 are described by the formulas (7) and (8), [C (NR ³ R ⁴ ) (OR ⁵ ) (NR ⁶ R ⁷ )] ⁺ (7) [C (NR ³ R ⁴ ) (SR ⁵ ) (NR ⁶ R ⁷ )] ⁺ (8), in which
R ³ to R ^{7 are} each independently

• - N (R ^{1 *} ) ₂ , or
• Straight-chain or branched alkyl having 1 to 20 C atoms,
• Straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
• Straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
• Saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
• - aryl having 6 to 12 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,

mean,
where one substituent or two substituents of the substituents R ³ to R ^{7 can be} completely substituted by halogen or one or more substituents R ³ , R ⁴ , R ⁶ and R ^{7 are} partially substituted by halogen, -OR ^{1 *} , -CN, - N (R ^{1 *} ) ₂ , -C (O) OR ^{1 *} , -OC (O) R ^{1 *} , -OC (O) OR ^{1 *} , -C (O) R ^{1 *} , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -SO ₂ X, -SR ^{1 *} , -S (O) R ^{1 *} and / or -SO ₂ R ^{1 *} may be substituted,
and wherein one or two non-adjacent and non-α-carbon atoms of R ³ to R ^{7 are} each independently selected from atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -SO ₂ O-, -C (O) -, -C (O) O-, -N ⁺ (R ^{1 *} ) ₂ -, -P (O) R ^{1 *} O-, -C (O) NR ^{1 *} -, -SO ₂ NR ^{1 *} -, -OP (O) R ^{1 *} O-, -P (O) (N (R ¹ ) ₂ ) NR ^{1 *} -, -P (R ^{1 *} ) ₂ = N- or -P (O) R ^{1 *} - can be replaced,
in which
R ^{1 are} each independently of one another not H or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl,
R ^{1 * are} each independently of one another not or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl and each X is independently halogen.

• – CN, OR^1* oder N(R^1*)₂,
• – geradkettiges oder verzweigtes Alkyl mit 1 bis 20 C-Atomen,
• – geradkettiges oder verzweigtes Alkenyl mit 2-20 C-Atomen und einer oder mehreren Doppelbindungen,
• – geradkettiges oder verzweigtes Alkinyl mit 2-20 C-Atomen und einer oder mehreren Dreifachbindungen,
• – gesättigtes oder teilweise ungesättigtes Cycloalkyl mit 3-7 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,
• – Aryl mit 6 bis 12 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,

bedeuten,
wobei ein Substituent oder zwei Substituenten der Substituenten R⁸ bis R¹³ vollständig mit Halogen substituiert sein kann/können oder ein oder mehrere Substituenten R⁸ bis R¹³ teilweise mit Halogen, -OR^1*, -CN, -N(R^1*)₂, -C(O)OR^1*, -OC(O)R^1*, -OC(O)OR^1*, -C(O)R^1*, -C(O)N(R¹)₂, -SO₂N(R¹)₂, -SO₂X, -SR^1*, -S(O)R^1* und/oder -SO₂R^1* substituiert sein kann/können,
und wobei ein oder zwei nicht benachbarte und nicht α-ständige Kohlenstoffatome der Reste R⁸ bis R¹³ jeweils unabhängig durch Atome und/oder Atomgruppierungen ausgewählt aus der Gruppe -O-, -S-, -S(O)-, -SO₂-, -SO₂O-, -C(O)-, -C(O)O-, -N⁺(R^1*)₂-, -P(O)R^1*O-, -C(O)NR^1*-, -SO₂NR^1*-, -OP(O)R^1*O-, -P(O)(N(R¹)₂)NR^1*-, -P(R^1*)₂=N- oder -P(O)R^1*- ersetzt sein können,
wobei
R¹ jeweils unabhängig voneinander für H nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht,
R^1* jeweils unabhängig voneinander für nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht und X jeweils unabhängig voneinander für Halogen steht.Preferred guanidinium cations for compounds of the formula (I) in which x is 3 are described by the formula (9), [C (N ^{R 8 R 9} ) (NR ¹⁰ R ¹¹ ) (NR ¹² R ¹³ )] ⁺ (9), in which
R ⁸ to R ^{13 are} each independently

• CN, OR ^{1 *} or N (R ^{1 *} ) ₂ ,
• Straight-chain or branched alkyl having 1 to 20 C atoms,
• Straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
• Straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
• Saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
• - aryl having 6 to 12 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,

mean,
where one substituent or two substituents of the substituents R ⁸ to R ^{13 can be} completely substituted by halogen or one or more substituents R ⁸ to R ^{13 are} partially substituted by halogen, -OR ^{1 *} , -CN, -N (R ^{1 *} ) ₂ , -C (O) OR ^{1 *} , -OC (O) R ^{1 *} , -OC (O) OR ^{1 *} , -C (O) R ^{1 *} , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -SO ₂ X, -SR ^{1 *} , -S (O) R ^{1 *} and / or -SO ₂ R ^{1 *} may be substituted,
and wherein one or two non-adjacent and non-α-carbon atoms of R ⁸ to R ^{13 are} each independently selected from atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -SO ₂ O-, -C (O) -, -C (O) O-, -N ⁺ (R ^{1 *} ) ₂ -, -P (O) R ^{1 *} O-, -C (O) NR ^{1 *} -, -SO ₂ NR ^{1 *} -, -OP (O) R ^{1 *} O-, -P (O) (N (R ¹ ) ₂ ) NR ^{1 *} -, -P (R ^{1 *} ) ₂ = N- or -P (O) R ^{1 *} - can be replaced,
in which
R ^{1 are} each independently of one another not H or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl,
R ^{1 * are} each independently of one another not or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl and each X is independently halogen.

wobei die Substituenten R^1' bis R^4' jeweils unabhängig voneinander

• – H bedeuten, wobei H für R^1' und R^4' ausgeschlossen ist,
• – geradkettiges oder verzweigtes Alkyl mit 1-20 C-Atomen bedeuten, welche auch fluoriert oder perfluoriert sein können, oder
• – geradkettiges oder verzweigtes Alkenyl mit 2-20 C-Atomen und einer oder mehreren Doppelbindungen bedeuten, welche auch fluoriert oder perfluoriert sein können, oder
• – geradkettiges oder verzweigtes Alkinyl mit 2-20 C-Atomen und einer oder mehreren Dreifachbindungen bedeuten, welche auch fluoriert sein können,
• – gesättigtes oder teilweise ungesättigtes Cycloalkyl mit 3-7 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,
• – Aryl mit 6 bis 12 C-Atomen, das mit geradkettigen oder verzweigten Alkylgruppen mit 1-6 C-Atomen substituiert sein kann,
• – gesättigtes, teilweise oder vollständig ungesättigtes Heteroaryl, Heteroaryl-C₁-C₆-alkyl oder Aryl-C₁-C₆-alkyl,

bedeuten,
wobei der Substituent R^2' jeweils unabhängig voneinander noch die Bedeutung F, Cl, Br, I, -CN, OR^1*, -N(R¹)₂, -P(O)(R^1*)₂, -P(O)(OR^1*)₂, -P(O)(N(R^1*)₂)₂, -C(O)R^1*, -C(O)OR^1*, -C(O)N(R¹)₂, -SO₂N(R¹)₂, -SO₂X, -SR^1*, -S(O)R^1*, und/oder -SO₂R¹ haben kann, unter der Bedingung, dass die Substituenten R^1' und R^4' in diesem Fall unabhängig voneinander geradkettiges oder verzweigtes Alkyl mit 1 bis 20 C-Atomen und/oder geradkettiges oder verzweigtes Alkenyl mit 2 bis 20 C-Atomen bedeuten und dass in diesem Fall der Substituent R^3' unabhängig von den Substituenten R^1' und R^4' H und/oder geradkettiges oder verzweigtes Alkyl mit 1 bis 20 C-Atomen und/oder geradkettiges oder verzweigtes Alkenyl mit 2 bis 20 C-Atomen bedeutet,
wobei die Substituenten R^1', R^2', R^3' und/oder R^4' zusammen ein Ringsystem bilden können,
wobei ein, zwei oder drei Substituenten R^1' bis R^4', aber nicht gleichzeitig R^1' und R^4', vollständig mit Halogen substituiert sein können oder ein oder mehrere der Substituenten R^1' bis R^4' teilweise mit Halogen, -OR^1*, -CN, -N(R¹)₂, -C(O)OR^1*, -OC(O)R^1*, -OC(O)OR^1*, -C(O)R^1*, -C(O)N(R¹)₂, -SO₂N(R¹)₂, -SO₂X, -SR^1*, -S(O)R^1* und/oder -SO₂R^1* substituiert sein können,
und wobei ein oder zwei nicht benachbarte und nicht α-ständige Kohlenstoffatome der Reste R^1' bis R^4' jeweils unabhängig durch Atome und/oder Atomgruppierungen ausgewählt aus der Gruppe -O-, -S-, -S(O)-, -SO₂-, -SO₂O-, -C(O)-, -C(O)O-, -N⁺(R^1*)₂-, -P(O)R^1*O-, -C(O)NR^1*-, -SO₂NR^1*-, -OP(O)R^1*O-, -P(O)(N(R¹)₂)NR^1*-, -P(R^1*)₂=N- oder -P(O)R^1*- ersetzt sein können
wobei
R¹ jeweils unabhängig voneinander für H nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht,
R^1* jeweils unabhängig voneinander für nicht oder teilweise oder perfluoriertes geradkettiges oder verzweigtes C₁- bis C₁₈-Alkyl; C₃- bis C₇-Cycloalkyl; unsubstituiertes oder substituiertes Phenyl steht,
R''' jeweils unabhängig voneinander für geradkettiges oder verzweigtes Alkyl mit 1 bis 6 C-Atomen steht,
X jeweils unabhängig voneinander für Halogen steht.Preferred heterocyclic cations for compounds of the formula (I) in which x is 3 are described by the formula (10), [HetN] ⁺ (10), wherein [HetN] ^{+ is} a heterocyclic cation selected from the group comprising

wherein the substituents R ^{1 '} to R ^{4' are} each independently

• - H, where H is excluded for R ^{1 '} and R ^4' ,
• - represent straight-chain or branched alkyl having 1-20 C atoms, which may also be fluorinated or perfluorinated, or
• - denote straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, which may also be fluorinated or perfluorinated, or
• Represent straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, which may also be fluorinated,
• Saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
• - aryl having 6 to 12 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
• Saturated, partially or completely unsaturated heteroaryl, heteroaryl-C ₁ -C ₆ -alkyl or aryl-C ₁ -C ₆ -alkyl,

mean,
wherein the substituent R ^{2 '} each independently of one another nor the meaning F, Cl, Br, I, -CN, OR ^{1 *} , -N (R ¹ ) ₂ , -P (O) (R ^{1 *} ) ₂ , -P ( O) (OR ^{1 *} ) ₂ , -P (O) (N (R ^{1 *} ) ₂ ) ₂ , -C (O) R ^{1 *} , -C (O) OR ^{1 *} , -C (O) N ( R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -SO ₂ X, -SR ^{1 *} , -S (O) R ^{1 *} , and / or -SO ₂ R ¹ may have, under the condition that the substituents R ^{1 '} and R ^4' in this case independently of one another denote straight-chain or branched alkyl having 1 to 20 C atoms and / or straight-chain or branched alkenyl having 2 to 20 C atoms and that in this case the substituent R ^{3 '} independently of the substituents R ^{1 '} and R ^4' denotes H and / or straight-chain or branched alkyl having 1 to 20 C atoms and / or straight-chain or branched alkenyl having 2 to 20 C atoms,
where the substituents R ^{1 '} , R ^2' , R ^{3 '} and / or R ^4' together can form a ring system,
where one, two or three substituents R ^{1 '} to R ^4' , but not simultaneously R ^{1 '} and R ^4' , may be completely substituted by halogen or one or more of the substituents R ^{1 '} to R ^{4' are} partially substituted by halogen, OR ^{1 *} , -CN, -N (R ¹ ) ₂ , -C (O) OR ^{1 *} , -OC (O) R ^{1 *} , -OC (O) OR ^{1 *} , -C (O) R ^{1 *} , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -SO ₂ X, -SR ^{1 *} , -S (O) R ^{1 *} and / or -SO ₂ R ^{1 *} can be substituted
and wherein one or two non-adjacent and non-α-carbon atoms of the radicals R ^{1 '} to R ^{4' are} each independently substituted by atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, - SO ₂ -, -SO ₂ O-, -C (O) -, -C (O) O-, -N ⁺ (R ^{1 *} ) ₂ -, -P (O) R ^{1 *} O-, -C ( O) NR ^{1 *} -, -SO ₂ NR ^{1 *} -, -OP (O) R ^{1 *} O-, -P (O) (N (R ¹ ) ₂ ) NR ^{1 *} -, -P (R ^{1 *} ) ₂ = N- or -P (O) R ^{1 *} - may be replaced
in which
R ^{1 are} each independently of one another not H or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl,
R ^{1 * are} each independently of one another not or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl,
R '''each independently of one another represents straight-chain or branched alkyl having 1 to 6 C atoms,
Each X is independently halogen.

A straight-chain or branched alkyl group having 1 to 18 C atoms is, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, furthermore pentyl, 1-, 2- or 3-methylbutyl, 1,1-, 1,2 or 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetra-acyl , n-pentadecyl, n-hexadecyl, n-heptadecyl or n-octadecyl. A straight-chain or branched alkyl group having 1 to 20 C atoms therefore consists of the stated alkyl groups having 1 to 18 C atoms plus n-nonadecyl or n-eicosyl. In a partially fluorinated alkyl group with 1 to 20 C atoms, the alkyl group has at least one F atom, but not all H atoms must be replaced by F atoms.

By a perfluoroalkyl group is meant an alkyl group whose H atoms are completely replaced by F atoms. Examples are described above.

A straight-chain or branched alkenyl having 2 to 20 C atoms, where not only the at least one double bond but also a plurality of double bonds may be present, is for example allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, iso- Pentenyl, hexenyl, heptenyl, octenyl, -C ₉ H ₁₇ , -C ₁₀ H ₁₉ to -C ₂₀ H ₃₉ ; preferably allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore preferred is 4-pentenyl, iso-pentenyl, hexenyl or decen-9-yl.

A straight-chain or branched alkynyl having 2 to 20 C atoms, in which not only the at least one triple bond but also multiple triple bonds may be present, is, for example, ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, furthermore 4-pentynyl, 3 Pentynyl, hexynyl, heptynyl, octynyl, -C ₉ H ₁₅ , -C ₁₀ H ₁₇ to -C ₂₀ H ₃₇ , preferably ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, 4-pentynyl, 3 Pentynyl or hexynyl.

Unsubstituted saturated or partially unsaturated cycloalkyl groups having 3-7 C atoms are therefore cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl or cycloheptenyl, which may be substituted by C ₁ - to C ₆ -alkyl groups, again the cycloalkyl group or the cycloalkyl group substituted with C ₁ to C ₆ alkyl groups also having halogen atoms such as F, Cl, Br or I, in particular F or Cl, or with -OR ¹ , -CN, -C (O) NR ¹ ₂ , -SO ₂ NR ¹ ₂ may be substituted, wherein R ^{1 has} a meaning given above.

Aryl having 6 to 12 carbon atoms denotes an aryl group having 6 to 12 carbon atoms and is, for example, phenyl, naphthyl or anthracenyl, which may be unsubstituted or substituted by a straight-chain or branched alkyl group having 1 to 6 carbon atoms. The substitution may be one or more times by the specified substituents and is preferably simple. Preferably, the phenyl group is substituted in the 4-position. Aryl having 6 to 12 C atoms is preferably phenyl which may be substituted by at least one straight-chain or branched alkyl group having 1 to 6 C atoms. In the case of the sulfonium cations of the formula (2), the phenyl group is preferably substituted by SR ¹ , where R ¹ has the meaning given above.

Aryl having 6 to 30 C atoms denotes an aryl group having 6 to 30 C atoms and is an aromatic group having a common aromatic electron system having 6 to 30 C atoms, optionally mono- or polysubstituted by R ^{1 *} , OR ¹ , N ( R ¹ ) ₂ , CN, NO ₂ or halogen substituted. An aryl group having 6 to 34 C atoms, preferably having 6 to 24 C atoms, is preferably substituted by R ^{1 *} , OR ¹ , N (R ¹ ) ₂ , CN or halogen substituted or unsubstituted 1, 2, 3 , 4-, 5- or 6-phenyl, 1-, 2-, 3-, 4-, 6-, 7- or 8-naphthyl, 1-, 2-, 3-, 4-, 6-, 7- or 8-phenanthrenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-anthracenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9 -, 10-, 11- or 12-tetracenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11- or 12-benzo [a ] anthracenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13- or 15-pentacenyl, 1-, 2 -, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11- or 12-chrysenyl, 1-, 2-, 3-, 4-, 5-, 6- , 7-, 8-, 9- or 10-pyrenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11- or 12-benzo [a] pyrenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-azulenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- , 8-, 9- or 10-fluoro-phenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11- or 12-perylenyl, 1- , 2-, 3-, 4-, 5-, 6- or 7-indenyl or 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-fluorenyl. R ¹ and R ^{1 *} have the meaning given above.

Aryl-C ₁ -C ₆ -alkyl is, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, where both the phenyl ring and the alkylene chain, as described above, partially or completely with halogens, in particular -F and / or -Cl, or partially substituted with -OR ¹ , -NR ¹ ₂ , -CN, -C (O) NR ¹ ₂ , -SO ₂ NR ¹ ₂ , wherein R ^{1 has} a meaning as described above.

Suitable substituents R ⁰ and R ² to R ^{13 of} the cations of the formulas (1), (4), (7) to (9) are preferably according to the invention: straight-chain or branched C ₁ - to C ₂₀ -, in particular straight-chain or branched C ₁ - to C ₁₄ -alkyl groups, saturated C ₃ - to C ₇ -cycloalkyl groups which may be substituted by straight-chain or branched C ₁ - to C ₆ -alkyl groups, or phenyl which is substituted by straight-chain or branched C ₁ - to C ₆ - Alkyl groups may be substituted.

The substituents R ⁰ and R ² in the cations of the formula (1) or (4) may be identical or different. In the case of cations of the formula (1), all substituents R ⁰ are preferably the same or equal to three and one substituent different. In the case of cations of the formula (4), preferably three or four substituents R ^{2 are} identical.

The substituents R ⁰ and R ² are particularly preferably methyl, ethyl, 2-methoxy-ethyl, ethoxy-methyl, 2-ethoxy-ethyl, isopropyl, 3-methoxy-propyl, propyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl or n-tetradecyl.

The substituents R ⁰¹ in the cations of the formula (2) or (3) may also be the same or different. In the case of cations of the formula (3), all substituents R ⁰¹ are preferably identical and preferably denote a straight-chain or branched alkyl group having 1 to 8 C atoms. In the case of cations of the formula (2), at least one substituent R ^{01 is} preferably phenyl or substituted phenyl. In the case of cations of the formula (2), the substituents R ^{01 are} preferably phenyl and / or phenyl substituted by SR ¹ , where R ¹ has the meaning given above or preferred meaning.

Preferred cations of the formula (2) are triphenylsulfonium, diphenyltolylsulfonium, diphenylethylsulfonium, diphenyl-2,2,2-trifluoroethylsulfonium, diphenyl-2-ethoxy-ethylsulfonium, diphenyl-2-chloroethylsulfonium, diphenyl-3-bromopropylsulfonium, diphenyl-3-chloropropylsulfonium , Diphenyl-3-cyanopropylsulfonium, diphenylallylsulfonium, diphenyl-4-pentenylsulfonium, diphenylpropargylsulfonium, diphenylbenzylsulfonium, diphenyl (p-cyanobenzyl) sulfonium, diphenyl (p-methylbenzyl) sulfonium, diphenyl (p-phenylthiobenzyl) sulfonium, diphenyl (3,3-dicyano -2-phenyl-2-propenyl) sulfonium, diphenyl (p-methylphenacyl) sulfonium, diphenyl (ethylcarboxy) methylsulfonium, diphenyl (n-octyl) sulfonium, diphenyl (n-octadecyl) sulfonium, diphenyl (ω-carboxytridecyl) sulfonium, diphenyl (3-oxypropyl) sulfonium, diphenyl (ω-carboxydodecyl) sulfonium, dihexyl-phenylsulfonium, ditolylphenylsulfonium, tritolylsulfonium, m- or p- (tert-butyl) phenyl-diphenylsulfonium, m- or p-methoxyphenyl-diphenylsulfonium, m- or p -CN Phen yl-diphenylsulfonium, m- or pC ₆ H ₁₃ S-phenyl-diphenylsulfonium, m- or pC ₆ H ₅ S-phenyl-diphenylsulfonium, tri (p-methoxyphenyl) sulfonium, tri [4- (4-acetylphenylsulfanyl) -phenyl] sulfonium , Tri (4-tert-butylphenyl) sulfonium.

Preferred cations of the formula (5) are diphenyliodonium, ditolyliodonium, phenyltolyliodonium, tolyl- (4-sec-butylphenyl) iodonium, di (p-tert-butylphenyl) iodonium, p-methoxyphenyl-phenyliodonium, di (p-methoxyphenyl) iodonium, m - or p-CN-phenyl-phenyliodonium, m- or p- (C ₆ H ₅ S) -phenyl-phenyliodonium or bis (dodecylphenyl) iodonium.

Preferred cations of the formula (6) are triphenylcarbenium, diphenyltolylcarbenium, ditolylphenylcarbenium, tritolylcarbenium, m- or p- (tert-butyl) phenyl-diphenylcarbenium, tri (p-tert-butyl) phenylcarbenium, m- or p-methoxyphenyl-diphenylcarbenium, m - or p-CN-phenyl-diphenylcarbenium, tri (p-CN-phenyl) carbenium, pC ₆ H ₅ S-phenyl-diphenylcarbenium, tri (p-methoxyphenyl) carbenium.

Up to four substituents of the guanidinium cation [C (NR ⁸ R ⁹ ) (NR ¹⁰ R ¹¹ ) (NR ¹² R ¹³ )] ⁺ may also be linked in pairs to form mono-, bi-, or polycyclic molecules.

wobei die Substituenten R⁸ bis R¹⁰ und R¹³ eine zuvor angegebene oder besonders bevorzugte Bedeutung haben können. Gegebenenfalls können die Carbocyclen oder Heterocyclen der zuvor angegebenen Guanidinium-Kationen vollständig mit Halogen substituiert sein oder teilweise mit Halogen, -OR¹, -CN, -N(R¹)₂, -C(O)OR¹, -OC(O)R¹, -OC(O)OR¹, -C(O)R¹, -C(O)N(R¹)₂, -SO₂N(R¹)₂, -C(O)X, -SO₃R¹, -SO₂X, -NO₂, -SR¹, -S(O)R¹, -SO₂R¹, -OR^1*, -C(O)OR^1*, -OC(O)R^1*, -OC(O)OR^1*, -C(O)R^1*, -SO₃R^1*, -SR^1*, -S(O)R^1* und/oder -SO₂R¹ substituiert sein, wobei R¹, R^1* und X eine zuvor angegebene Bedeutung haben.Without limiting the generality, the formula (9) includes the following examples:

where the substituents R ⁸ to R ¹⁰ and R ^{13 may have} a previously given or particularly preferred meaning. Optionally, the carbocycles or heterocycles of the above guanidinium cations may be fully substituted with halogen or partially substituted with halogen, -OR ¹ , -CN, -N (R ¹ ) ₂ , -C (O) OR ¹ , -OC (O) R ¹ , -OC (O) OR ¹ , -C (O) R ¹ , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -C (O) X, -SO ₃ R ¹ , -SO ₂ X, -NO ₂ , -SR ¹ , -S (O) R ¹ , -SO ₂ R ¹ , -OR ^{1 *} , -C (O) OR ^{1 *} , -OC (O) R ^{1 *} , -OC (O) OR ^{1 *} , -C (O) R ^{1 *} , -SO ₃ R ^{1 *} , -SR ^{1 *} , -S (O) R ^{1 *} and / or -SO ₂ R ¹ be substituted, wherein R ¹ , R ^{1 *} and X have the meaning given above.

Up to four substituents of the thiouronium or uronium cation [C (NR ³ R ⁴ ) (YR ⁵ ) (NR ⁶ R ⁷ )] ⁺ with Y = O or S may also be linked in pairs such that mono-, bi- or polycyclic Molecules are created.

worin Y = S oder O bedeutet
und wobei die Substituenten R³, R⁵ und R⁶ eine zuvor angegebene oder besonders bevorzugte Bedeutung haben können.Without limiting the generality, the formulas (7) and (8) include the following examples:

wherein Y = S or O means
and wherein the substituents R ³ , R ⁵ and R ^{6 may have} a previously given or particularly preferred meaning.

Optionally, the carbocycles or heterocycles of the aforesaid thiouronium or uronium cations may be fully substituted with halogen or partially substituted with halo, -OR ¹ , -CN, -N (R ¹ ) ₂ , -C (O) OR ¹ , -OC (O) R ¹ , -OC (O) OR ¹ , -C (O) R ¹ , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -C (O) X , -SO ₃ R ¹ , -SO ₂ X, -NO ₂ , -SR ¹ , -S (O) R ¹ , -SO ₂ R ¹ , -OR ^{1 *} , -C (O) OR ^{1 *} , -OC (O) R ^{1 *} , -OC (O) OR ^{1 *} , -C (O) R ^{1 *} , -SO ₃ R ^{1 *} , -SR ^{1 *} , -S (O) R ^{1 *} and / or -SO ₂ R ^{1 be} substituted, wherein R ¹ , R ^{1 *} and X have the meaning given above.

The substituents R ³ to R ¹³ are each, independently of one another, preferably a straight-chain or branched alkyl group having 1 to 10 C atoms. The substituents R ³ and R ⁴ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ¹⁰ and R ¹¹ and R ¹² and R ¹³ in compounds of the formulas (7) to (9) may be identical or different. Particularly preferably, R ³ to R ^{13 are} each independently methyl, ethyl, 2-methoxy-ethyl, ethoxy-methyl, n-propyl, 3-methoxy-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl , Phenyl or cyclohexyl, most preferably methyl, ethyl, n-propyl, iso-propyl or n-butyl.

Suitable substituents R ^{1 '} and R ^4' of compounds of the formula (10) according to the invention are preferably: straight-chain or branched C ₁ - to C ₂₀ , in particular straight-chain or branched C ₁ - to C ₁₂ -alkyl groups, saturated C ₃ - to C ₇ -cycloalkyl groups which may be substituted by straight-chain or branched C ₁ - to C ₆ -alkyl groups or phenyl which may be substituted by straight-chain or branched C ₁ - to C ₆ -alkyl groups.

Suitable substituents R ^{2 '} and R ^3' of compounds of the formula (10) according to the invention in this case in addition to H are preferably: straight-chain or branched C ₁ - to C ₂₀ , in particular straight-chain or branched C ₁ - to C ₁₂ alkyl groups.

The substituents R ^{1 '} and R ^4' are each, in each case independently of one another, particularly preferably methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl or benzyl. They are very particularly preferably methyl, ethyl, n-butyl or n-hexyl. In pyrrolidinium, piperidinium or indolinium compounds, the two substituents R ^{1 '} and R ^{4' are} preferably different.

The substituent R ^{2 '} or R ^3' is, in each case independently of one another, in particular H, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, tert-butyl, cyclohexyl, phenyl or benzyl. R ^{2 '} is particularly preferably H, methyl, ethyl, isopropyl, n-propyl, n-butyl or sec-butyl. Very particular preference is given to R ^{2 '} and R ^3' H.

In R ¹ , C ₃ - to C ₇ -cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.

In R ¹ , R ^{1 *} and R ^{1 **} is substituted phenyl, by C ₁ - to C ₆ -alkyl, C ₁ - to C ₆ -alkenyl, F, Cl, Br, I, -C ₁ -C ₆ - Alkoxy, -C (O) R ", -NR" ₂ , -SR ", -S (O) R", -SO ₂ R "or SO ₂ NR" _2, substituted phenyl, where R ''is a non, partially or perfluorinated C ₁ - to C ₆ -alkyl or C ₃ - to C ₇ -cycloalkyl, for example, o-, m- or p-methylphenyl, o-, m- or p-ethylphenyl, , m- or p-propylphenyl, o-, m- or p-isopropylphenyl, o-, m- or p-tert-butylphenyl, o-, m- or p-methoxyphenyl, o-, m- or p-ethoxyphenyl , o-, m- or p-fluorophenyl, o-, m- or p-chlorophenyl, o-, m- or p-bromophenyl, o-, m- or p-iodophenyl, more preferably 2,3-, 2, 4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3 , 5-difluorophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichlorophenyl, 2,3-, 2,4-, 2,5- , 2,6-, 3,4- or 3,5-dibromophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethoxyphenyl, 5- Fluoro-2-methylphenyl, 3,4,5-trimethoxyphenyl or the like r 2,4,4-trimethylphenyl.

In R ^{1 '} to R ^4' is understood as a heteroaryl saturated or unsaturated mono- or bicyclic heterocyclic radical having 5 to 13 ring members, where 1, 2 or 3 N and / or 1 or 2 S or O atoms may be present and the heterocyclic radical is partially substituted by halogen, -OR ¹ , -CN, -N (R ¹ ) ₂ , -C (O) OR ¹ , -OC (O) R ¹ , -OC (O) OR ¹ , -C ( O) R ¹ , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -C (O) X, -SO ₃ R ¹ , -SO ₂ X, -NO ₂ , - SR ¹ , -S (O) R ¹ , -SO ₂ R ¹ , -OR ^{1 *} , -C (O) OR ^{1 *} , -OC (O) R ^{1 *} , -OC (O) OR ^{1 *} , - C (O) R ^{1 *} , -SO ₃ R ^{1 *} , -SR ^{1 *} , -S (O) R ^{1 *} and / or -SO ₂ R ^{1 be} substituted, wherein R ¹ , R ^{1 *} and X is a previously have meaning indicated.

The heterocyclic radical or Het is preferably substituted or unsubstituted 2- or 3-furyl, 2- or 3-thienyl, 1-, 2- or 3-pyrrolyl, 1-, 2-, 4- or 5-imidazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-isothiazolyl, 2-, 3- or 4-pyridyl, 2-, 4-, 5- or 6-pyrimidinyl, furthermore preferably 1,2,3-triazole-1, -4- or -5-yl, 1,2,4-triazole 1-, 4- or -5-yl, 1- or 5-tetrazolyl, 1,2,3-oxadiazol-4 or -5-yl 1,2,4-oxadiazol-3 or -5-yl, 1,3,4-thiadiazol-2 or -5-yl, 1,2,4-thiadiazol-3 or -5-yl, 1,2,3-thiadiazol-4 or -5-yl, 2- , 3-, 4-, 5- or 6-2H-thiopyranyl, 2-, 3- or 4-4H-thiopyranyl, 3- or 4-pyridazinyl, pyrazinyl, 2-, 3-, 4-, 5-, 6 - or 7-Benzofuryl, 2-, 3-, 4-, 5-, 6- or 7-benzothienyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-1H-indolyl, 1 , 2-, 4- or 5-benzimidazolyl, 1-, 3-, 4-, 5-, 6- or 7-benzopyrazolyl, 2-, 4-, 5-, 6- or 7-benzoxazolyl, 3-, 4-, 5-, 6- or 7-benzisoxazolyl, 2 , 4-, 5-, 6- or 7-benzthiazolyl, 2-, 4-, 5-, 6- or 7-benzisothiazolyl, 4-, 5-, 6- or 7-benz-2,1,3- oxadiazolyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinolinyl, 1-, 3-, 4-, 5-, 6-, 7- or 8-isoquinolinyl, 1 -, 2-, 3-, 4- or 9-carbazolyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-acridinyl, 3-, 4-, 5 -, 6-, 7- or 8-cinnolinyl, 2-, 4-, 5-, 6-, 7- or 8-quinazolinyl or 1-, 2- or 3-pyrrolidinyl.

By heteroaryl-C ₁ -C ₆ -alkyl is now understood analogously to aryl-C ₁ -C ₆ -alkyl, for example pyridinyl-methyl, pyridinyl-ethyl, pyridinyl-propyl, pyridinyl-butyl, pyridinyl-pentyl, pyridinyl-hexyl, wherein furthermore the previously described heterocycles can be linked in this way with the alkylene chain.

wobei die Substituenten R^1' bis R^4' jeweils unabhängig voneinander eine zuvor beschriebene Bedeutung haben.HetN ⁺ is preferred

wherein the substituents R ^{1 '} to R ^4' each independently have a meaning as described above.

For the technical applications of ionic liquids, as described in detail later, compounds of the formula (I) are suitable whose cations correspond to the formulas (1), (4), (7), (8), (9) and (10) as described above or with substituents described as being preferred.

For the technical applications of ionic liquids, as described in detail later, preference is given to compounds of the formula (I) whose cations correspond to the formulas (1), (4) and (10), as described above or with substituents described as being preferred are.

Another object of the invention are therefore preferably compounds of formula (I), as described above, in which Cat is selected from the group of organic cations of the formula (1), (4) or (10), as described above.

Particularly suitable cations of the formulas (1), (4) and (10) for compounds of the formula (I) are selected from the group tetraalkylammonium, tetraalkylphosphonium, 1,1-dialkylpyrrolidinium, 1-alkyl-1-alkoxyalkylpyrrolidinium or 1,3-dialkylimidazolium wherein the alkyl groups or the alkoxy group in the alkoxyalkyl group may each independently have 1 to 10 carbon atoms. Most preferably, the alkyl groups have 1 to 6 carbon atoms and the alkoxy group 1 to 3 carbon atoms. The alkyl groups in the tetraalkylammonium or in the tetraalkylphosphonium can therefore be identical or different. Preferably, three alkyl groups are the same and one alkyl group is different or two alkyl groups are the same and the other two are different. Preferred tetraalkylammonium cations are, for example, trimethyl (ethyl) ammonium, triethyl (methyl) ammonium, tripropyl (methyl) ammonium, tributyl (methyl) ammonium, tripentyl (methyl) ammonium, trihexyl (methyl) ammonium, triheptyl (methyl) ammonium, trioctyl ( methyl) ammonium, trinonyl (methyl) ammonium, tridecyl (methyl) ammonium, trihexyl (ethyl) ammonium, ethyl (trioctyl) ammonium, propyl (dimethyl) ethyl ammonium, butyl (dimethyl) ethyl ammonium, methoxyethyl (dimethyl) ethyl ammonium, methoxyethyl (diethyl) methylammonium, methoxyethyl (dimethyl) propylammonium, ethoxyethyl (dimethyl) ethylammonium. Particularly preferred quaternary ammonium cations are propyl (dimethyl) ethylammonium and / or methoxyethyl (dimethyl) ethylammonium.

Preferred tetraalkylphosphonium cations are, for example, trimethyl (ethyl) phosphonium, triethyl (methyl) phosphonium, tripropyl (methyl) phosphonium, tributyl (methyl) phosphonium, tripentyl (methyl) phosphonium, trihexyl (methyl) phosphonium, triheptyl (methyl) phosphonium, trioctyl ( methyl) phosphonium, trinonyl (methyl) phosphonium, tridecyl (methyl) phosphonium, trihexyl (ethyl) phosphonium, ethyl (trioctyl) phosphonium, propyl (dimethyl) ethyl phosphonium, butyl (dimethyl) ethyl phosphonium, methoxyethyl (dimethyl) ethyl phosphonium, methoxyethyl (diethyl) methylphosphonium, methoxyethyl (dimethyl) propylphosphonium, ethoxyethyl (dimethyl) ethylphosphonium. Particularly preferred quaternary phosphonium cations are propyl (dimethyl) ethylphosphonium and / or methoxyethyl (dimethyl) ethylphosphonium.

Preferred 1,1-dialkylpyrrolidinium cations are, for example, 1,1-dimethylpyrrolidinium, 1-methyl-1-ethylpyrrolidinium, 1-methyl-1-propylpyrrolidinium, 1-methyl-1-butylpyrrolidinium, 1 methyl-1-pentyl pyrrolidinium, 1-methyl-1-hexyl-pyrrolidinium, 1-methyl-1-heptyl-pyrrolidinium, 1-methyl-1-octyl-pyrrolidinium, 1-methyl-1-nonyl-pyrrolidinium, 1-methyl-1-decyl pyrrolidinium, 1,1-diethyl-pyrrolidinium, 1-ethyl-1-propyl-pyrrolidinium, 1-ethyl-1-butyl-pyrrolidinium, 1-ethyl-1-pentyl-pyrrolidinium, 1-ethyl-1-hexyl-pyrrolidinium, 1-Ethyl-1-heptyl-pyrrolidinium, 1-ethyl-1-octyl-pyrrolidinium, 1-ethyl-1-nonyl-pyrrolidinium, 1-ethyl-1-decyl-pyrrolidinium, 1,1-dipropyl-pyrrolidinium, 1 Propyl 1-methylpyrrolidinium, 1-propyl-1-butylpyrrolidinium, 1-propyl-1-pentylpyrrolidinium, 1-propyl-1-hexylpyrrolidinium, 1-propyl-1-heptylpyrrolidinium, 1- Propyl-1-octyl-pyrrolidinium, 1-propyl-1-nonyl-pyrrolidinium, 1-propyl-1-decyl-pyrrolidinium, 1,1-dibutyl-pyrrolidinium, 1-butyl-1-methyl-pyrrolidinium, 1-butyl 1-pentyl-pyrrolidinium, 1-butyl-1-hexyl-pyrrolidinium, 1-butyl-1-heptyl-pyrrolidinium, 1-butyl-1-octyl-pyrrolidinium, 1-butyl-1-nonyl-pyrrolidinium, 1-butyl 1-decylpyrrolidinium, 1,1-dipentyl -pyrrolidinium, 1-pentyl-1-hexylpyrrolidinium, 1-pentyl-1-heptylpyrrolidinium, 1-pentyl-1-octylpyrrolidinium, 1-pentyl-1-nonylpyrrolidinium, 1-pentyl-1-decyl pyrrolidinium, 1,1-dihexylpyrrolidinium, 1-hexyl-1-heptylpyrrolidinium, 1-hexyl-1-octylpyrrolidinium, 1-hexyl-1-nonylpyrrolidinium, 1-hexyl-1-decylpyrrolidinium , 1,1-dihexyl-pyrrolidinium, 1-hexyl-1-heptyl-pyrrolidinium, 1-hexyl-1-octyl-pyrrolidinium, 1-hexyl-1-nonyl-pyrrolidinium, 1-hexyl-1-decyl-pyrrolidinium, 1 , 1-diheptylpyrrolidinium, 1-heptyl-1-octylpyrrolidinium, 1-heptyl-1-nonylpyrrolidinium, 1-heptyl-1-decylpyrrolidinium, 1,1-dioctylpyrrolidinium, 1-octyl-1 nonylpyrrolidinium, 1-octyl-1-decylpyrrolidinium, 1-1-dinonylpyrrolidinium, 1-nony-1-decylpyrrolidinium or 1,1-didecylpyrrolidinium. Very particular preference is given to 1-butyl-1-methylpyrrolidinium or 1-propyl-1-methylpyrrolidinium.

Preferred 1-alkyl-1-alkoxyalkylpyrrolidinium cations are, for example, 1-methoxyethyl-1-methylpyrrolidinium, 1-methoxyethyl-1-ethylpyrrolidinium, 1-methoxyethyl-1-propylpyrrolidinium, 1-methoxyethyl-1-butyl pyrrolidinium, 1-ethoxyethyl-1-methylpyrrolidinium, 1-ethoxymethyl-1-methylpyrrolidinium. Very particular preference is given to 1-methoxyethyl-1-methylpyrrolidinium. Methoxyethyl means CH ₃ OCH ₂ CH ₂ -. Ethoxyethyl means CH ₃ CH ₂ OCH ₂ CH ₂ -.

Preferred 1,3-dialkylimidazolium cations are, for example, 1-ethyl-3-methylimidazolium, 1-methyl-3-propylimidazolium, 1-butyl-3-methylimidazolium, 1-methyl-3-pentylimidazolium, 1 Ethyl 3-propylimidazolium, 1-butyl-3-ethylimidazolium, 1-ethyl-3-pentylimidazolium, 1-butyl-3-propylimidazolium, 1,3-dimethylimidazolium, 1,3- Diethylimidazolium, 1,3-dipropylimidazolium, 1,3-dibutylimidazolium, 1,3-dipentylimidazolium, 1,3-dihexylimidazolium, 1,3-diheptylimidazolium, 1,3-dioctylimidazolium, 1,3-dinonylimidazolium, 1,3- Didecylimidazolium, 1-hexyl-3-methyl-imidazolium, 1-heptyl-3-methyl-imidazolium, 1-methyl-3-octyl-imidazolium, 1-methyl-3-nonyl-imidazolium, 1-decyl-3-methyl imidazolium, 1-ethyl-3-hexyl-imidazolium, 1-ethyl-3-heptyl-imidazolium, 1-ethyl-3-octyl-imidazolium, 1-ethyl-3-nonyl-imidazolium or 1-decyl-3-ethyl- imidazolium. Particularly preferred cations are 1-ethyl-3-methyl-imidazolium, 1-butyl-3-methyl-imidazolium or 1-methyl-3-propyl-imidazolium.

Particularly preferred 1-alkenyl-3-alkylimidazolium cations are 1-allyl-3-methylimidazolium or 1-allyl-2,3-dimethylimidazolium.

Very particularly preferred compounds of the formula (I) for industrial applications of ionic liquids are compounds whose cations correspond to the formula (10) where HetN ⁺ imidazolium, pyrrolidinium or pyridinium, with substituents R ^{1 '} to R ^4' , each independently each have a specified or preferred meaning. Within the group of cations of the formula (10), the imidazolium cation is particularly preferred, where the substituents R ^{1 '} to R ^4' have the abovementioned meaning or preferred meaning or are preferably 1,3-dialkylimidazolium, 1-alkenyl 3-alkylimidazolium or 1-alkoxyalkyl-3-alkylimidazolium as previously described.

Particularly preferred compounds of the formula (I) for the industrial applications of ionic liquids have cations selected from the group consisting of 1-butyl-1-methylpyrrolidinium, 1-ethyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1 Butyl 2,3-dimethylimidazolium, 1- (2-methoxyethyl) -3-methylimidazolium, 1-butyl-3-methylimidazolium, tributylmethylammonium, tetra-n-butylammonium, tributylmethylphosphonium, tetra-phenylphosphonium, tetra-butylphosphonium, Diethylmethylsulfonium, S-ethyl-N, N, N ', N'-tetramethylisothiouronium, 1-allyl-3-methylimidazolium, 1-allyl-2,3-dimethylimidazolium, 1-cyanomethyl-3-methylimidazolium, 1- (2-cyanoethyl ) -3-methylimidazolium, 1-methyl-3-propynylimidazlium, 1-butyl-4-methylpyridinum and 1,1-dimethylpyrrolidinium.

The inorganic cations of the compounds of formula (I) wherein x is 1 or 2 are selected from NO ⁺ , solvated proton [H ⁺ ], a cation of a group 1, 2, 3, 4, 5, 6, 7 element , 8, 9, 10, 11 and / or 12 of the Periodic Table, a complex cation containing at least one element of group 3, 4, 5, 6, 7, 8, 9, 10, 11 and / or 12 of the Periodic Table, containing a cation Al, Ga, In, Ge, Sn, Pb, Sb or Bi or a mixture of these cations selected.

The inorganic cations of the compounds of the formula (I) in which x is 3 are selected from a cation of an element of group 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and / or 12 of the Periodic Table, a complex cation containing at least one element of group 3, 4, 5, 6, 7, 8, 9, 10, 11 and / or 12 of the Periodic Table, a cation containing Al, Ga, In, Ge, Sn, Pb , Sb or Bi or a mixture of these cations selected.

The proton [H ⁺ ] is present in particular in the form of a solvated proton, ie in a complex with an organic solvent or with water. The proton particularly preferably accumulates water and can therefore be written in the form [H ₃ O] ⁺ . A suitable organic solvent for solvation is diethyl ether.

When the term [H ⁺ ] is used in the present specification, this term also encompasses complexes with organic solvents, for example diethyl ether, or with water, more preferably this term encompasses [H ₃ O] ⁺ .

Compounds of formula (I) containing inorganic cations, such as. For example, [H] ⁺ , K ⁺ , Na ⁺ are particularly suitable for the preparation of compounds of formula (I) containing organic cations or alternative inorganic cations. Compounds of the formula (I) with metal cations or complex cations are also particularly suitable as catalysts or phase transfer catalysts.

All statements on compounds of the formula (I) as described above apply correspondingly to the compounds of the formula (I-1) which are defined below.

Another object of the invention is the preparation of compounds of formula (I), as described above or described as preferred.

Accordingly, another object of the invention is the preparation of compounds of formula (I), as described above or described as preferred, in which x is 3 and m is 0, characterized in that
a compound of the formula (II) C _n F _{(2n + 1)} Li (II), in which
n is an integer from 1 to 12, where n is preferably a number from 1 to 8,
is reacted with a compound of the formula (III), BH ₃ · X (III), wherein X is a coordinating organic molecule stabilizing the trihydrido-borane complex,
the conditions of the reaction being chosen such that both the water content and the oxygen content amount to a maximum of 1000 ppm,
and optionally subsequently at least one cation exchange with a compound of the formula (IV) CatA (IV), is carried out,
wherein Cat means another organic or inorganic cation according to claim 1 or 2, and
A represents an anion selected from Cl ^- , Br ^- , I ^- , [CO ₃ ] ^2- , [R ₁ COO] ^- , [R ₁ SO ₃ ] ^- , [R ₂ COO] ^- , [R ₂ SO ₃ ] ^- , [R ₁ OSO ₃ ] ^- , [BF ₄ ] ^- , [PF ₆ ] ^- , [(R ₂ ) ₂ P (O) O] ^- or [R ₂ P (O) O ₂ ] ^2- , wherein each R ₁ is independently straight-chain or branched alkyl having 1 to 4 C atoms, R ₂ each independently of one another means straight-chain or branched perfluorinated alkyl having 1 to 4 carbon atoms, wherein the electroneutrality of the salts of the formula CatA is to be observed.

The compound of the formula (II) can be prepared from fluoroalkanes C _n F _{(2n + 1)} H by reaction with an organolithium compounds, where n has the abovementioned meaning, such as. In DE 10128703 A1 described.

Alternatively, the compound of formula (II) may be prepared by reacting the corresponding iodides C _n F _{(2n + 1)} I with an organolithium compound at low temperatures, such as in N. Yu. Adonin, VV Bardin, H.-J. Frohn, Z. Anorg. Gen. Chem., 2007, 633, 647-652 described. In the iodides n has a previously mentioned meaning.

Suitable organolithium compounds are commercially available and can be selected, for example, from the group n-butyl lithium, sec-butyl lithium, tert-butyl lithium, methyl lithium, ethyl lithium or phenyllithium in organic solvents such. As tetrahydrofuran, toluene, dialkyl ethers (eg., Diethyl ether) or in a mixture with hexane or cyclohexane are selected, whereby also their combination with the ligands TMEDA (tetramethylenediamine), PMDTA (N, N, N ', N', N ' 'Pentamethyldiethylenetriamine), monoglyme, diglyme or sparteine can increase the reactivity of the organolithium compound.

Preferably, the compound of formula (II) is prepared as previously described using (n- or tert-) butyllithium.

Trihydridoborane complexes of formula (III) as described above are commercially available or may be prepared by known methods. The coordinating organic molecule X is preferably 1,4-dioxane, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, diglyme, triglyme or dimethyl sulfide. Particularly preferably, a tetrahydrofuran complex of the formula (III) is used, prepared in parallel and reacted further without further purification or generated in situ, as described below.

In a preferred embodiment of this process, the trihydridoborane complex of the formula (III) is prepared from an alkali metal tetrahydridoborate and reacted further without further purification.

Accordingly, a process is the subject of the present invention as described above, wherein the compound of formula (III) is prepared from an alkali metal tetrahydridoborate.

Alkali metals are the metals lithium, sodium, potassium, cesium or rubidium. Preferred alkali metals are potassium and / or sodium. A particularly suitable alkali metal tetrahydridoborate is sodium borohydride. For example, the alkali metal tetrahydridoborate is suspended in tetrahydrofuran, a suitable coordinating organic molecule as described above, and then reacted with a trialkylsilyl chloride. The reaction mixture is preferably stirred at room temperature and then reacted further. Preferably, it is stirred for about 15 hours.

Alternatively, the alkali metal tetrahydridoborate may also be reacted with a trialkylsilyl bromide, with acids or oxidants such as iodine.

The alkyl groups of the trialkylsilyl chloride or trialkylsilyl bromide are each independently a linear or branched alkyl group having 1 to 10 carbon atoms. A preferred trialkylsilyl chloride is trimethylsilyl chloride.

In a preferred embodiment of the process as described above, the compound of formula (III) is prepared and cooled to -78 ° C to -110 ° C. In parallel, the organic solvent is cooled to -78 ° C to -110 ° C and degassed, then the compound of formula (II) is prepared in situ, wherein a corresponding haloalkane is condensed and the organolithium compound is slowly added dropwise with stirring on the publication of N. Yu. Adonin, VV Bardin, H.-J. Frohn, Z. Anorg. Gen. Chem., 2007, 633, 647-652 , Then the compound of formula (III) is added and the reaction mixture is slowly heated to temperatures between -20 ° C and room temperature and worked up accordingly, as described below or preferably described in the execution section. Preference is given to heating to room temperature.

An alternative method for preparing compounds of the formula (I) as described above or described as preferred in which x is 3 and m is 0 is characterized in that a compound of the formula (IIa) C _n F _{(2n + 1)} Si (CH ₃ ) ₃ (IIa), in which
n is an integer from 1 to 12, preferably an integer from 1 to 8,
is reacted with a compound of the formula (III) in the presence of a fluoride anion source, BH ₃ · X (III), wherein X is a coordinating organic molecule stabilizing the trihydrido-borane complex,
wherein the conditions of the reaction are chosen such that both the water content and the oxygen content amount to a maximum of 1000 ppm.

The compounds of the formula (IIa) are commercially available or can be prepared by methods known from the literature (see, for example, US Pat. VA Petrov, Tetrahedron Letters, 2001, vol. 42, pp. 3267-3269 ).

Another alternative method for preparing compounds of the formula (I) as described above or described as preferred in which x is 3 and m is 0, 1, 2, 3 or 4, is characterized in that a Grignard compound of the formula (IIb) C _n F _{(2n + 1) -m} H _m MgHlg (IIb), in which
n is an integer from 1 to 12, preferably an integer from 1 to 8, m is 0, 1, 2, 3 or 4, and Hg is a halogen, preferably Br or I,
is reacted with a compound of the formula (III), BH ₃ · X (III), wherein X is a coordinating organic molecule stabilizing the trihydrido-borane complex,
wherein the conditions of the reaction are chosen such that both the water content and the oxygen content amount to a maximum of 1000 ppm.

The synthesis of fluorinated Grignard compounds is described in the literature, e.g. In M. Hudlicky "Chemistry of Organic Fluorine Compounds", Ellis Horwood Ltd., 1976 ,

The reaction of the compounds of the formula (II), (IIa) or (IIb) with compounds of the formula (III) is preferably carried out in an organic solvent. The organic solvent preferably corresponds to the coordinating organic molecule of the compound of the formula (III) as described above or described as being preferred.

It is preferred to mix the starting materials for the preparation of the compounds of formula (I) in which x is 3, as described above, in an inert gas atmosphere whose oxygen content is at most 1000 ppm. It is particularly preferred if the oxygen content is less than 500 ppm, very particularly preferably not more than 100 ppm. The water content of the reagents and the inert gas atmosphere is at most 1000 ppm. It is particularly preferred if the water content of the reagents and of the atmosphere is less than 500 ppm, very particularly preferably not more than 100 ppm. The conditions concerning the water content and the oxygen content do not apply to the work-up after a successful reaction or to a salting reaction.

In the preparation according to the invention of the compounds of the formula (I) in which x is 3 as described above, it is preferred, when the reaction of the reactants is followed by a purification step, to obtain the end product of the formula (I) as described above Separate by-products or reaction products. Suitable purification steps include the separation of volatile components by distillation or condensation, extraction with an organic solvent, precipitation by addition of an organic solvent, salification, or a combination of these methods. Any known separation method can be used or combined for this purpose.

A preferred method for the purification is, for example, the reaction of the resulting reaction mixture with a corresponding carbonate (Me) ₂ CO ₃ . If this alkali metal cation corresponds to the desired cation of the compound of the formula (I) in which x is 3, then no further salification is necessary. The compound of formula (I) is separated, for example by distillation of the organic solvent and optionally recrystallized or by extraction with a suitable solvent.

If a cation exchange is desired, then in a classical metathesis reaction, reaction is continued with a compound of the formula (IV), as described above. Isolation of the previously prepared compound of the formula (I) is not necessary for this purpose and is preferably not carried out.

Compounds of the formula (IV) CatA (IV), wherein Cat is an organic or inorganic cation as described above, and
A represents an anion selected from Cl ^- , Br ^- , I ^- , [CO ₃ ] ^2- , [R ₁ COO] ^- , [R ₁ SO ₃ ] ^- , [R ₂ COO] ^- , [R ₂ SO ₃ ] ^- , [R ₁ OSO ₃ ] ^- , [BF ₄ ] ^- , [PF ₆ ] ^- , [(R ₂ ) ₂ P (O) O] ^- or [R ₂ P (O) O ₂ ] ^2- , R _{1 being in} each case independently of one another straight-chain or branched alkyl having 1 to 4 C atoms, R _{2 in} each case independently of one another denotes straight-chain or branched perfluorinated alkyl having 1 to 4 C atoms, the electroneutrality of the salts of the formula CatA being to be observed,
are commercially available or can be synthesized by methods known in the art.

The cation exchange by reaction with compounds of the formula (IV), as described above, is carried out in water or in organic solvents or a mixture of these solvents, the reaction being carried out in water or in a solvent mixture containing water at temperatures from 0 ° to 50 ° C , preferably at 0 ° to 25 ° C. Particularly preferred is reacted at room temperature.

The reaction in organic solvents takes place at temperatures between -80 ° C and 100 ° C. Suitable organic solvents are, for example, selected from acetonitrile, propionitrile, acetone, dioxane, dichloromethane, dimethoxyethane, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or dialkyl ethers, for example diethyl ether or methyl tert-butyl ether. Preference is given to reacting in acetonitrile, propionitrile, acetone, diethyl ether, dichloromethane or a mixture of acetonitrile / dichloromethane or acetonitrile / diethyl ether.

R ₂ is in each case independently of one another preferably trifluoromethyl, pentafluoroethyl or nonafluorobutyl, particularly preferably trifluoromethyl or pentafluoroethyl.

R ₁ is in each case independently of one another preferably methyl, ethyl or n-butyl, particularly preferably methyl or ethyl.

The anion of the compounds of the formula (IV) is preferably Cl ^- , Br ^- , I ^- , [CH ₃ C (O) O] ^- , [CH ₃ SO ₃ ] ^- , [CF ₃ C (O) O] ^- , [CF ₃ SO ₃ ] ^- , [CH ₃ OSO ₃ ] ^- , [BF ₄ ] ^- , [PF ₆ ] ^- , [C ₂ H ₅ OSO ₃ ] ^- , [(C ₂ F ₅ ) ₂ P (O) O] ^- or [C ₂ F ₅ P (O) O ₂ ] ^2- , more preferably Cl ^- , Br ^- , I ^- , [CH ₃ SO ₃ ] ^- , [CH ₃ OSO ₃ ] ^- , [CF ₃ COO ] ^- , [CF ₃ SO ₃ ] ^- , [(C ₂ F ₅ ) ₂ P (O) O] ^- or [BF ₄ ] ^- . The anion in compounds of the formula (IV) is very particularly preferably Cl ^- , Br, [CF ₃ SO ₃ ] ^- or [BF ₄ ] ^- .

The salting reaction may again be followed by a purification step or the isolation, as described above and known to the person skilled in the art.

Further details on the reaction conditions of the process according to the invention are described in the examples section.

Another object of the invention is a process for the preparation of compounds of formula (I), as described above, in which x is 1, characterized in that
a compound of the formula (I) in which x represents 3, corresponding to the formula (I-1) Cat [(C _n F _{(2n + 1) -m} H _m ) BH ₃ ] (I-1), where Cat, n and m have the meaning given above, is reacted with a cyanating reagent,
wherein the conditions of the reaction are chosen such that the oxygen content is at most 1000 ppm,
and optionally subsequently at least one cation exchange with a compound of the formula (IV) CatA (IV), is carried out,
wherein Cat means another organic or inorganic cation and
A represents an anion selected from Cl ^- , Br ^- , I ^- , [CO ₃ ] ^2- , [R ₁ COO] ^- , [R ₁ SO ₃ ] ^- , [R ₂ COO] ^- , [R ₂ SO ₃ ] ^- , [R ₁ OSO ₃ ] ^- , [BF ₄ ] ^- , [PF ₆ ] ^- , [HSO ₄ ] ^1- , [NO ₃ ] ^- , [(R ₂ ) ₂ P (O) O] ^- or [R ₂ P (O) O ₂ ] ^2- wherein R ₁ is independently straight-chain or branched alkyl having 1 to 4 C atoms, R ₂ is independently of one another straight-chain or branched perfluorinated alkyl having 1 to 4 C atoms , where the electroneutrality of the Salts of formula CatA is observed. The anion of the compound of formula (IV) in this metathesis reaction is preferably Cl ^- , Br ^- , I ^- , [CH ₃ SO ₃ ] ^- , [CH ₃ OSO ₃ ] ^- , [CF ₃ COO] ^- , [CF ₃ SO ₃ ] ^- , [(C ₂ F ₅ ) ₂ P (O) O] ^- or [BF ₄ ] ^- . The anion of the compound of formula (IV) is particularly preferably in this metathesis reaction Cl ^- , Br ^- , [CF ₃ SO ₃ ] ^- or [BF ₄ ] ^- .

The compounds of the formula (I) wherein x is 3, corresponding to compounds of the formula (I-1), can be prepared by the method as described above.

Cyanation reagents are known to the person skilled in the art. These include, for example, alkali metal cyanides or trialkylsilyl cyanides. A preferred cyanating reagent for the preparation of the compounds of the formula (I) are trialkylsilyl cyanides.

Trialkylsilyl cyanides are commercially available or can be generated in situ. In the process according to the invention, preference is given to using a purified trialkylsilyl cyanide. The alkyl groups of the trialkylsilyl cyanide are each independently a linear or branched alkyl group having 1 to 10 carbon atoms.

The alkyl groups of the trialkylsilyl cyanide may be the same or different. Preferably, the alkyl groups are the same. Examples of suitable trialkylsilyl cyanides are therefore trimethylsilyl cyanide, triethylsilyl cyanide, triisopropylsilyl cyanide, tripropylsilyl cyanide, octyldimethylsilyl cyanide or tributylsilyl cyanide. Particularly preferred is trimethylsilyl cyanide used, which is commercially available or is prepared by known methods.

Many preparation methods for the synthesis of trialkylsilyl cyanides are described.

Trialkylsilyl cyanides can be prepared, for example, from an alkali metal cyanide and a trialkylsilyl chloride. In EP 76413 it is described that this reaction was carried out in the presence of an alkali metal iodide and in the presence of N-methylpyrrolidone. In EP 40356 it is described that this reaction was carried out in the presence of a heavy metal cyanide. In WO 2008/102661 it is described that this reaction was carried out in the presence of iodine and zinc iodide.

In WO 2011/085966 it is described that this reaction can be carried out in the presence of an alkali metal iodide and optionally iodine. In this case, sodium cyanide and sodium iodide or potassium cyanide and potassium iodide are preferably used, the alkali metal iodide preferably being added in a molar amount of 0.1 mol / l, based on 1 mol / l alkali metal cyanide and trialkylsilyl chloride. Generally, this method of preparation is based on the description of MT Reetz, I. Chatziiosifidis, Synthesis, 1982, p. 330 ; JK Rasmussen, SM Heilmann and LR Krepski, The Chemistry of Cyanotrimethylsilanes in GL Larson (Ed.) "Advances in Silicon Chemistry", Vol. 1, p. 65-187, JAI Press Inc., 1991 or WO 2008/102661 ,

The trialkylsilyl cyanide is preferably used in excess, preferably in an amount of 2.6 to 7 mol, based on the compound of the formula (I-1).

It is preferred to mix the starting materials for the preparation of the compounds of the formula (I) in which x is 1, in an inert gas atmosphere whose oxygen content is at most 1000 ppm. It is particularly preferred if the oxygen content is less than 500 ppm, very particularly preferably not more than 100 ppm. The water content of the reagents and the inert gas atmosphere is preferably at most 1000 ppm. The conditions concerning the water content and the oxygen content do not apply to the work-up after a successful reaction or to a salting reaction.

The reaction for preparing the compounds of the formula (I) in which x is 1 preferably takes place in an autoclave, because the reaction is preferably carried out under pressure, for example at 2 to 10 bar, more preferably at 2 to 7 bar.

In a preferred embodiment of the process for the preparation of the compounds of the formula (I) in which x is 1, as described above, a compound of the formula (I-1) is introduced into an autoclave and admixed with the cyanating reagent, preferably trialkylsilyl cyanide. Subsequently, the reaction mixture is heated to 200 ° C, whereby a pressure of 7 bar sets. A preferred reaction time is 5 to 30 hours.

In the preparation according to the invention of the compounds of the formula (I) in which x is 1, it is preferred if the reaction of the reactants is followed by a purification step in order to separate the end product of the formula (I) from by-products or reaction products as described above , Suitable purification steps include the separation of volatile components by distillation or condensation, extraction with an organic solvent, precipitation by addition of an organic solvent, salification, or a combination of these methods. Any known separation method can be used or combined for this purpose.

A preferred purification method for the autoclave reaction described above is the removal of all volatiles of the reaction mixture, followed by one or more extractions in suitable organic solvents. In each case insoluble constituents are filtered off.

Suitable organic solvents are, for example, acetonitrile, propionitrile, acetone, dioxane, dichloromethane, dimethoxyethane, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or dialkyl ethers, for example diethyl ether or methyl tert-butyl ether, or alcohol, for example methanol, ethanol or isopropanol. Preferably, diethyl ether is selected as the solvent.

If a cation exchange is desired below, then in a classical metathesis reaction, reaction is continued with a compound of the formula (IV), as described above. Isolation of the previously prepared compound of the formula (I) is not necessary for this, but would be possible. It may be advantageous to first react with an acid and to extract and further react the compound of formula (I) wherein Cat represents [H] ⁺ .

Further details on the reaction conditions of the process according to the invention are described in the examples section.

An alternative process for the preparation of compounds of the formula (I), as described above, in which x denotes 1, is characterized in that a compound of the formula (V) Cat [(C _n F _{(2n + 1) -m} H _m ) BF (CN) ₂ ] (V), where Cat, n and m are as defined above,
with an alkali metal hydride in the presence of an electrophilic reagent affinity to fluoride anions,
the conditions of the reaction being chosen such that both the water content and the oxygen content amount to a maximum of 1000 ppm,
and optionally subsequently at least one cation exchange with a compound of the formula (IV) CatA (IV), is carried out,
wherein Cat means another organic or inorganic cation and
A represents an anion selected from Cl ^- , Br ^- , I ^- , [CO ₃ ] ^2- , [R ₁ COO] ^- , [R ₁ SO ₃ ] ^- , [R ₂ COO] ^- , [R ₂ SO ₃ ] ^- , [R ₁ OSO ₃ ] ^- , [BF ₄ ] ^- , [PF ₆ ] ^- , [HSO ₄ ] ^1- , [NO ₃ ] ^- , [(R ₂ ) ₂ P (O) O] ^- or [R ₂ P (O) O ₂ ] ^2- wherein R ₁ is independently straight-chain or branched alkyl having 1 to 4 C atoms, R ₂ is independently of one another straight-chain or branched perfluorinated alkyl having 1 to 4 C atoms , whereby the electroneutrality of the salts of the formula CatA is to be considered. The anion of the compound of formula (IV) in this metathesis reaction is preferably Cl ^- , Br ^- , I ^- , [CH ₃ SO ₃ ] ^- , [CH ₃ OSO ₃ ] ^- , [CF ₃ COO] ^- , [CF ₃ SO ₃ ] ^- , [(C ₂ F ₅ ) ₂ P (O) O] ^- or [BF ₄ ] ^- . The anion of the compound of formula (IV) is particularly preferably in this metathesis reaction Cl ^- , Br ^- , [CF ₃ SO ₃ ] ^- or [BF ₄ ] ^- .

The compounds of the formula (V) as described above can be prepared by processes known from the literature, for example as described in US Pat WO 2011/085966 described.

Particularly suitable alkali metal hydrides are potassium hydride and / or sodium hydride. Most preferably, potassium hydride is used.

Without being bound by theory, the mechanism of the nucleophilic substitution reaction is assumed for this process variant.

It has been shown that the addition of an electrophilic reagent that has a good affinity for F ^- accelerates the substitution. The term "affinity for F ^- " means that the reagent used preferably binds to the F ^- . The bond may be a covalent bond or a bond that occurs through electrostatic interaction.

In a preferred embodiment of this process variant, the (F ^- ) affine electrophilic reagent is a lithium salt or a magnesium salt.

Suitable lithium salts are lithium bromide, lithium iodide, lithium chloride, lithium triflate, lithium perchlorate or lithium tetrafluoroborate.

A suitable magnesium salt is magnesium triflate.

In a particularly preferred embodiment of this process variant, lithium chloride or lithium bromide is used as the electrophilic reagent.

The reaction of the compounds of the formula (V), as described above, with the alkali metal hydride is preferably carried out in the presence of an organic solvent, for example in the presence of ethers. Preferred ethers are tetrahydrofuran, diethyl ether, methyl tert-butyl ether or dimethoxyethane. Particular preference is given to using tetrahydrofuran.

Preferably, this reaction takes place at temperatures between 10 ° C and 200 ° C, in particular between 15 ° C and 150 ° C, more preferably at 60 ° C to 90 ° C, most preferably at 60 ° C to 80 ° C instead. The reaction takes place in an inert gas atmosphere, preferably with the exclusion of water and oxygen, as described above. The comments apply accordingly.

A preferred purification method for the above-described reaction with alkali metal hydride is the addition of water to the reaction mixture and the subsequent removal of all volatiles from the reaction mixture.

If a cation exchange is desired below, then in a classical metathesis reaction, reaction is continued with a compound of the formula (IV), as described above. Isolation of the previously prepared compound of the formula (I) is not necessary for this, but would be possible.

Further details on reaction conditions of the process are described in the examples section.

Another object of the invention is a process for the preparation of compounds of formula (I), as described above, in which x is 1 or 2, characterized in that
a compound of the formula (I) in which x represents 3, corresponding to the formula (I-1) Cat [(C _n F _{(2n + 1) -m} H _m ) BH ₃ ] (I-1), where Cat, n and m are as defined above,
is reacted with a compound of formula (VI) or with a mixture of the acid of formula (VI) and its salt, RC (O) OH (VI), where R is a straight-chain or branched alkyl group or perfluoroalkyl group having 1 to 6 C atoms,
wherein the conditions of the reaction are chosen such that the oxygen content is at most 1000 ppm,
below, the compound of formula (VIIa) or formula (VIIb) resulting from this reaction Cat [(C _n F _{(2n + 1) -m} H _m ) BH ₂ OC (O) -R] (VIIa), Cat [(C _n F _{(2n + 1) -m} H _m ) BH (OC (O) -R) ₂ ] (VIIb), is reacted with a cyanating reagent without or under microwave irradiation, preferably with a power of at least 220 W,
wherein Cat, n, m and R have one of the meanings mentioned above, and
the conditions of the reaction being chosen such that both the water content and the oxygen content amount to a maximum of 1000 ppm,
and optionally subsequently at least one cation exchange with a compound of the formula (IV) CatA (IV), is carried out,
wherein Cat means another organic or inorganic cation according to claim 1 or 2 and
A represents an anion selected from Cl ^- , Br ^- , I ^- , [CO ₃ ] ^2- , [R ₁ COO] ^- , [R ₁ SO ₃ ] ^- , [R ₂ COO] ^- , [R ₂ SO ₃ ] ^- , [R ₁ OSO ₃ ] ^- , [BF ₄ ] ^- , [PF ₆ ] ^- , [HSO ₄ ] ^1- , [NO ₃ ] ^- , [(R ₂ ) ₂ P (O) O] ^- or [R ₂ P (O) O ₂ ] ^2- wherein R ₁ is independently straight-chain or branched alkyl having 1 to 4 C atoms, R ₂ is independently of one another straight-chain or branched perfluorinated alkyl having 1 to 4 C atoms , whereby the electroneutrality of the salts of the formula CatA is to be considered. The anion of the compound of formula (IV) in this metathesis reaction is preferably Cl ^- , Br ^- , I ^- , [CH ₃ SO ₃ ] ^- , [CH ₃ OSO ₃ ] ^- , [CF ₃ COO] ^- , [CF ₃ SO ₃ ] ^- , [(C ₂ F ₅ ) ₂ P (O) O] ^- or [BF ₄ ] ^- . The anion of the compound of formula (IV) is particularly preferably in this metathesis reaction Cl ^- , Br ^- , [CF ₃ SO ₃ ] ^- or [BF ₄ ] ^- .

The compounds of formula (I-1) can be prepared by a method as described above.

The acids of formula (VI) and their salts are commercially available or can be prepared by methods known to those skilled in the art. In the compounds of the formula (VI), R is preferably a linear or branched alkyl group having 1 to 8 C atoms or a linear or branched perfluoroalkyl group having 1 to 8 C atoms. In the compounds of the formula (VI), R is particularly preferably a linear or branched alkyl group or perfluoroalkyl group having 1 to 4 C atoms. In the compounds of the formula (VI), R is very particularly preferably methyl, n-propyl or trifluoromethyl.

In the production of the substances of the formula (VIIa) and (VIIb), as described above, the conditions of the reaction are chosen such that both the water content and the oxygen content amount to a maximum of 1000 ppm.

In a preferred embodiment of the preparation of the compounds of the formula (VIIa) and (VIIb), the compounds of the formula (I-1) are dissolved in a suitable organic solvent and cooled to 0 ° C. Then, with stirring, the compound of formula (VI) is added. The resulting hydrogen is discharged as appropriate, as it is suitable for the apparatus. The reaction mixture is then warmed to room temperature and all volatiles are removed.

Suitable solvents for the reaction with compounds of the formula (VI) are dialkyl ethers, for example diethyl ether or methyl tert-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, CH ₂ Cl ₂ or chloroform or acetonitrile. A preferred solvent is CH ₂ Cl ₂ , chloroform or acetonitrile.

It may be followed by a suitable purification as described above. The comments apply accordingly. In a preferred embodiment, the volatiles are removed and the residue obtained is dissolved in tetrahydrofuran and treated with the salt of the acid of formula (VI). It is also advantageous to heat this mixture for about one hour at 70 ° C to 100 ° C, preferably at 75 ° C.

The compounds of formula (VIIa) and (VIIb) can also be isolated. It may also be advantageous at this stage of the reaction to make a corresponding cation exchange with a compound of the formula (IV), as described in detail above, so that the solubility of the compound of the formula (VIIa) and (VIIb) is given in the chosen cyanating reagent, if you want to work without another organic solvent.

Suitable cyanating reagents are known to the person skilled in the art. The statements on preferred cyanation reagents and their preparation also apply accordingly to this process.

The reaction of the compounds of the formula (VIIa) and (VIIb) with the cyanating reagent, preferably trialkylsilyl cyanide, preferably takes place in a closed device with or without microwave irradiation, preferably with a power of at least 220 W. The reaction time when using microwave irradiation is preferably 100 to 200 minutes, more preferably 150 minutes. Without Microwave irradiation, the reaction time is preferably 7 to 30 hours at preferred temperatures of 70 ° C to 150 ° C. The temperature data refer to the temperature of the heating medium.

In one embodiment of the process, as described above or described as preferred, it is advantageous if the reaction of the compound of the formula (VIIa) or (VIIb), as described above or described as preferred, takes place without the presence of an organic solvent. However, it is also possible to carry out the reaction in the presence of an organic solvent.

Suitable solvents are dialkyl ethers, for example diethyl ether or methyl tert-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, diglyme, acetonitrile or a mixture of these solvents. A preferred solvent is tetrahydrofuran.

In a preferred embodiment of the process according to the invention for preparing compounds of the formula (I) in which x 2 is as described above, the reaction of the compound of the formula (VIIa) with trimethylsilyl cyanide takes place.

In a preferred embodiment of the process according to the invention for preparing compounds of the formula (I) in which x denotes 1 as described above, the reaction of the compound of the formula (VIIb) with trimethylsilyl cyanide takes place.

A preferred purification method for the microwave irradiation reaction described above is the removal of all volatiles of the reaction mixture, followed by one or more extractions in suitable organic solvents. In each case insoluble constituents are filtered off.

Suitable organic solvents are, for example, acetonitrile, propionitrile, acetone, dioxane, dichloromethane, dimethoxyethane, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or dialkyl ethers, for example diethyl ether or methyl tert-butyl ether, or alcohol, for example methanol, ethanol or isopropanol. The solvents acetone and diethyl ether are preferably selected and removed again.

Preference is then followed by reaction of the residues obtained with an aqueous solution of a corresponding carbonate (Me) ₂ CO ₃ and / or a corresponding hydrogen carbonate MeHCO ₃ , Me corresponding to the cation of an alkali metal. If this alkali metal cation corresponds to the desired cation of the compound of the formula (I) in which x is 2, then no further salification is necessary. The compound of formula (I) is then appropriately isolated as known to those skilled in the art.

If a cation exchange is desired below, then in a classical metathesis reaction, reaction is continued with a compound of the formula (IV), as described above. Isolation of the previously prepared compound of the formula (I) is not necessary for this, but would be possible.

Further details on the reaction conditions of the process according to the invention are described in the examples section.

An alternative method of preparing compounds of formula (I) wherein x is 2 is characterized by the use of a cyanide source, such as a cyanide source. B. alkali metal cyanides, Tetralkylammoniumcyanide or trialkylsilyl cyanides, with a compound of formula (VIII), (C _n F _{(2n + 1) -m} H _m ) BH ₂ .X (VIII), is implemented,
in which
n is an integer from 1 to 12, preferably an integer from 1 to 8,
m is 0, 1, 2, 3 or 4 and
X is a coordinating organic molecule which stabilizes the dihydrido-borane complex.

Correspondingly suitable coordinating organic molecules have been described previously. The statements apply mutatis mutandis to the compounds of formula (VIII).

The compounds of formula (VIII) can be prepared by reacting the compounds of formula (I-1) with a trialkylsilyl chloride or bromide, by reaction with an acid or by reaction with an electrophilic reagent such as iodine.

Suitable reaction conditions have previously been described for compounds of the formula (III) and apply correspondingly.

Further details on the reaction conditions of the process according to the invention are described in the examples section.

Another object of the invention are the compounds of formula (VIIa) or of formula (VIIb), which arise as intermediates, Cat [(C _n F _{(2n + 1) -m} H _m ) BH ₂ OC (O) -R] (VIIa), Cat [(C _n F _{(2n + 1) -m} H _m ) BH (OC (O) -R) ₂ ] (VIIb), in which
R is a straight-chain or branched alkyl group or perfluoroalkyl group having 1 to 6 C atoms and
Cat represents an alkali metal cation or a tetraalkylammonium cation,
wherein the alkyl groups in the tetraalkylammonium cation each independently have 1 to 10 carbon atoms.

Of course, these compounds of the invention may be used as starting materials for further metathesis reactions, such that the cation Cat is not intrinsically restricted in the compounds of formula (VIIa) or (VIIb). The general statements on the possible inorganic and organic cations and the preferred embodiments for the compounds of the formula (I) in which x is 1 or 2, apply correspondingly.

Compounds of the formula (I) with alkali metal cations, in particular lithium compounds of the formula (I) in which x is 1, are suitable not only for suitability as starting material for the preparation of further compounds of the formula (I), but also as conducting salt in electrochemical cells.

Preferred electrochemical cells are lithium batteries, lithium ion batteries or lithium capacitors.

The corresponding lithium salts can also be used in combination with other conductive salts or additives in the electrochemical cells without further restriction. Depending on the concentration in an electrolyte, the corresponding lithium salts can also be used as an additive.

The corresponding lithium salts can be used singly or in mixtures in analogy to alternative lithium compounds known for this application.

The compounds of the formula (I) with organic cations, in particular where x is 1 or 2, as described above or described as preferred, are suitable as additive for polymers, as solvent or solvent additive, as catalyst for organic synthesis, as phase transfer Catalyst, as an electrolyte component in electrochemical, electronic or optoelectronic devices, as a fluorosurfactant, as a heat carrier, as a release agent, extractant, as a plasticizer, as a lubricant or component of lubricating oils or fats, as a hydraulic fluid or additive for hydraulic fluids.

The compounds of the formula (I) in which x is 3 and the compounds of the formula (VIII) as described above or described as being preferred are particularly suitable as reducing agents, preferably as reducing agents in organic synthesis.

The salts of the formula (I) are hydrophobic and show better solubility in organic solvents than the comparable hydrido or hydridocyano borates.

Another object of the invention is therefore the use of compounds of formula (I) in which x is 1 or 2, with organic cations, as described above or preferably described, as an additive for polymers, solvents or solvent addition, as a catalyst for the organic Synthesis, as a phase transfer catalyst, as an electrolyte component in electrochemical, electronic or optoelectronic devices, as a fluorosurfactant, as a heat carrier, as a release agent, extractant, as a plasticizer, as a lubricant or component of lubricating oils or fats, as a hydraulic fluid or additive for hydraulic fluids.

The compounds of the formula (I) having an organic cation as described above may also be ionic liquids. The definition of an ionic liquid has been previously described.

When using the compounds of the formula (I) in which x is 1 or 2 with organic cations, as described above, as solvents, they are suitable for any type of reaction known to those skilled in the art, for example for transition metal- or enzyme-catalyzed reactions , such as As hydroformylation reactions, oligomerization reactions, esterifications or isomerizations, this list does not claim to be exhaustive.

When used as an extractant, the compounds of formula (I) wherein x is 1 or 2 may be used with organic cations as described above to separate reaction products, but also to separate impurities, depending on the solubility of the particular component the ionic liquid. In addition, the ionic liquids can also serve as separation media in the separation of several components, for example in the distillative separation of several components of a mixture. Further possible applications are the use as plasticizers in polymer materials or as an additive in fuel cells.

Further fields of application of the compounds of the formula (I) in which x denotes 1 or 2 with organic cations according to this invention are solvents for carbohydrate-containing solids, in particular biopolymers and their derivatives or degradation products. In addition, these new compounds can be used as lubricants, working fluids for machinery such as compressors, pumps or hydraulic devices.

Another area of application is the field of particle or nanomaterial synthesis, in which these ionic liquids can act as a medium or additive.

The compounds of the formula (I) in which x is 1 or 2, as described above, with organic cations are also preferably suitable as a constituent of electrolyte formulations.

A further subject of the invention is accordingly an electrolyte formulation comprising at least one compound of the formula (I) in which x denotes 1 or 2, as described above. The other constituents of the electrolyte formulation are known to the person skilled in the art and are not restricted in this regard.

A further subject of the invention is likewise an electrochemical or optoelectronic device containing at least one compound of the formula (I) in which x denotes 1 or 2, as described above or described as preferred or alternatively an electrolyte formulation containing at least one compound of the formula (I) , Like previously described.

Preferred electrochemical devices are, for example, devices for energy storage, preferably double-layer capacitors, synonymous supercapacitors.

For use in double-layer capacitors, a high conductivity is required. The compounds of the formula (I) according to the invention in which x denotes 1 with organic cations as described above fulfill this criterion and can therefore be used alone or in mixtures with other solvents or conducting salts. Suitable solvents are those selected from the group of organic carbonates (eg, ethylene carbonate, propylene carbonate and their derivatives, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, etc.), organic carboxylic esters (eg, γ-butyrolactone, methyl formate, methyl acetate, ethyl acetate, ethyl propionate , Methyl propionate, methyl butyrate, ethyl butyrate, etc.), organic carboxylic acid amides (e.g., dimethylformamide, methylformamide, formamide, etc.), organic ether (e.g., 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydrofuran derivatives, 1.3 Dioxolane, dioxane, dioxolane derivatives, etc.) or other aprotic solvents (e.g., acetonitrile, sulfolane, dimethylsulfoxide, nitromethane, phosphoric triesters, trimethoxymethane, 3-methyl-2-oxazolidinone, etc.). Solvent mixtures, such as. Ethylene carbonate / dimethyl carbonate (EC / DMC) can also be used.

These organic cation compounds of formula (I) as described above can be used in electrolyte formulations with conventional conductive salts. Suitable z. B. Electrolytic formulations with conductive salts selected from the group LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ or Li [(C ₂ F _{5) 3} PF _3] and mixtures thereof.

Examples of preferred optoelectronic devices include solar cells, including photovoltaic cells that are not only excited by sunlight, optical detectors, photoreceptors, photodiodes, photodetectors, transistors, light-emitting devices, lasers or charging diodes. Preferred optoelectronic devices are devices that generate energy.

Particularly preferred devices are solar cells, in particular dye solar cells. The structure of a solar cell and the materials used for it are known in the art and, for example, in the publications WO 2011/085966 . WO 2012/163489 and WO 2013/010641 described.

The following embodiments are intended to illustrate the invention without limiting it. The invention is correspondingly executable throughout the claimed area. Based on the example also possible variants can be derived.

Working technique and devices:

Syntheses at elevated pressure are carried out in a Roth high pressure laboratory autoclave (100 ml working volume, empty space 140 ml with heating hood 10 S, high pressure fine valve, indicating pressure gauge with measuring range 0-160 bar and Bourdon tube measuring system). Temperature data in the autoclave tests refer to the temperatures set on the heating hood.

For the recording of ¹ H, ¹¹ B, ¹³ C, ¹⁹ F and ³¹ P NMR spectra, an Avance 200 MHz or a DPX 400 MHz spectrometer from Bruker is used for the reaction controls. Isolated products are analyzed using a Bruker Avance 500 MHz or DRX 300 MHz spectrometer. The ¹¹ B NMR spectra are referenced to BF ₃ · Et ₂ O (0 ppm, external) and ¹⁹ F NMR spectra to CFCl ₃ (0 ppm, external). The ³¹ P NMR spectra are referenced to the signal of 85% phosphoric acid (0 ppm, external). NMR spectroscopic studies of the isolated compounds are carried out with deuterated solvents. The ¹ H and ¹³ C NMR spectra are referenced to the residual proton or ¹³ C signals.
Acetone-d _6: ¹ H: 2.05 ppm, ¹³ C: 29.90 ppm.
CDCl _3: ¹ H: 7.25 ppm, ¹³ C: 77.16 ppm.
CD ₂ Cl _2: ¹ H: 5:32 ppm, ¹³ C: 54.00 ppm.
CD3CN: ¹ H: 1.94 ppm, ¹³ C: 1:32 ppm.

Unless a deuterated solvent is indicated, acetone-d6 is used.

The elemental analyzes to determine the percentages of carbon, nitrogen and hydrogen are carried out with a Euro EA 3000 from HEKAtech Analysentechnik.

The thermoanalytical investigations are carried out in the form of DSC measurements (differential scanning calorimetry) with a DSC 823 from Mettler Toledo. For this purpose, the substances are investigated in an aluminum crucible at a heating rate of 5 ° C / min or at a cooling rate of 10 ° C min ^-1 .

The IR spectra are measured using a Nicolet 380 FT-IR spectrometer from Thermo Electron Corporation. The images are taken on the ATR technique (attenuated total reflection) on a diamond crystal. The Raman spectra are recorded using a Bruker IFS 120HR FT spectrometer with a FRA 106 Raman module in a range from -200 cm ^-1 to 4000 cm ^-1 . In this case, an Nd-YAG laser with an excitation wavelength of 1064 nm is used.

The mass spectra are recorded on an Autoflex II LRF Bruker Daltonics TOF (time of flight) mass spectrometer. For the ionization of the substances, the MALDI method (matrix assisted laser desorption / ionization) is used.

GC-MS investigations of the reduction experiments are recorded with a Gas Chromatograph Trace 1310 coupled with an ISO QD single quadrupole mass spectrometer from ThermoScientific. The evaluation is done automatically by the program Chromeleon 7.

Cyclic voltammograms are measured with an Autolab PGSTAT30 at 0.015 V / s in a window of -3.15 to 2.25V. The starting point is -0.5 V. The conducting salt used is [TBA] [PF ₆ ] (0.1 M), which is dissolved in CH ₃ CN (3 mL). The working electrode is a Classy carbon electrode (⌀ = 3 mm) used, the counter electrode is a platinum wire and the reference electrode is a silver electrode with 0.01 M AgNO ₃ in 0.1 M [TBA] [PF ₆ ] in CH ₃ CN.

Examples:

Example 1: Synthesis of 1-ethyl-3-methylimidazolium pentafluoroethyl trihydridoborate; [EMIM] [C ₂ F ₅ BH ₃ ]

¹H-NMR (500.13 MHz, Aceton-d₆) δ, ppm: 8.96 (s, 1H, CH, H³), 7.70 (dd, ³J(¹H, ¹H) ≈ ³J(¹H, ¹H) ≈ 1.80 Hz, 1H, CH, H⁴), 7.62 (dd, ³J(¹H, ¹H) ≈ ³J(¹H, ¹H) ≈ 1.80 Hz, 1H, CH, H⁴), 4.34 (q, ³J(¹H, ¹H) = 7.25 Hz, 2H, CH₂, H²), 3.99 (s, 3H, CH₃, H⁵), 1.53 (t, ³J(¹H, ¹H) = 7.32 Hz, 3H, CH₃, H¹), 0.94-0.25 (m, 3H, ¹⁰BH₃), 0.65 (qtq, ¹J(¹¹B, ¹H) = 84.63 Hz, ³J(¹⁹F, ¹H) = 27.35 Hz, ⁴J(¹⁹F, ¹H) = 3.75 Hz, 3H, ¹¹BH₃).
¹H{¹⁰B}-NMR (500.13 MHz, Aceton-d₆) δ, ppm: 8.96 (s, 1H, CH, H³), 7.69 (dd, ³J(¹H, ¹H) ≈ ³J(¹H, ¹H) ≈ 1.70 Hz, 1H, CH, H⁴), 7.62 (dd, ³J(¹H, ¹H) ≈ ³J(¹H, ¹H) ≈ 1.55 Hz, 1H, CH, H⁴), 4.34 (q, ³J(¹H, ¹H) = 7.34 Hz, 2H, CH₂, H²), 3.99 (s, 3H, CH₃, H⁵), 1.53 (t, ³J(¹H, ¹H) = 7.37 Hz, 3H, CH₃, H¹), 0.60 (tq, ³J(¹⁹F, ¹H) = 27.41 Hz, ⁴J(¹⁹F, ¹H) = 3.78 Hz, 3H, BH₃), 0.57 (qtq, ¹J(¹¹B, ¹H) = 84.72 Hz, ³J(¹⁹F, ¹H) = 27.35 Hz, ⁴J(¹⁹F, ¹H) = 3.63 Hz, 3H, BH₃).
¹H{¹¹B}-NMR (500.13 MHz, Aceton-d₆) δ, ppm: 8.96 (s, 1H, CH, H³), 7.70 (dd, ³J(¹H, ¹H) ≈ ³J(¹H, ¹H) ≈ 1.78 Hz, 1H, CH, H⁴), 7.62 (dd, ³J(¹H, ¹H) ≈ ³J(¹H, ¹H) ≈ 1.78 Hz, 1H, CH, H⁴), 4.34 (q, ³J(¹H, ¹H) = 7.32 Hz, 2H, CH₂, H²), 3.99 (s, 3H, CH₃, H⁵), 1.53 (t, ³J(¹H, ¹H) = 7.33 Hz, 3H, CH₃, H¹), 0.83-0.35 (m, 3H, ¹⁰BH₃), 0.57 (tq, ³J(¹⁹F, ¹H) = 27.40 Hz, ⁴J(¹⁹F, ¹H) = 3.77 Hz, 3H, ¹¹BH₃).
¹⁰B{¹H}-NMR (53.73 MHz, Aceton-d₆) δ, ppm: –33.0 (t, ²J(¹⁹F, ¹⁰B) = 6.1 Hz).
¹¹B-NMR (160.46 MHz, Aceton-d₆) δ, ppm: –32.9 (qt, ¹J(¹¹B, ¹H) = 84.6 Hz, ²J(¹⁹F, ¹¹B) = 18.5 Hz).
¹¹B{¹H}-NMR (160.46 MHz, Aceton-d₆) δ, ppm: –32.9 (t, J(¹⁹F, ¹¹B) = 18.3 Hz).
¹³C{¹H}-NMR (125.76 MHz, Aceton-d₆) δ, ppm: 136.9 (s, 1C, CH, C-H³), 133.8 (tqq, ¹J(¹⁹F, ¹³C) = 242.2 Hz, ²J(¹⁹F, ¹¹B) = 52.8 Hz, ²J(¹⁹F, ¹³C) = 35.2 Hz, 1C, CF₂), 124.4 (s, 1C, CH, C-H⁴) 123.7 (qtq, ¹J(¹⁹F, ¹³C) = 286.0 Hz, ²J(¹⁹F, ¹³C) = 35.3 Hz, ³J(¹⁹F, ¹¹B) = 3.3 Hz, 1C, CF₃), 122.8 (s, 1C, CH, C-H⁴), 45.5 (s, 1C, CH₂, C-H²), 36.5 (s, 1C, CH₃, C-H⁵), 15.4 (s, 1C, CH₃, C-H¹).
¹⁹F-NMR (188.12 MHz, Aceton-d₆) δ, ppm: –84.6 (s, 3F, CF₃), –111.1 (qq, ²J(¹⁹F, ¹¹B) = 18.5 Hz, ²J(¹⁹F, ¹H) = 27.4 Hz, 2F, CF₂).
¹⁹F{¹H}-NMR (188.12 MHz, Aceton-d₆) δ, ppm: –84.6 (s, 3F, CF₃), –111.1 (q, ²J(¹⁹F, ¹¹B) = 18.3 Hz, 2F, CF₂).

Elementaranalyse, %: gefunden (berechnet): C 39.84 (39.38), H 5.84 (5.78), N 11.90 (11.48).

Dynamische Viscosität, η, mPa·s: 37.6 (20°C), 26.7 (30°C), 19.7 (40°C), 15.0 (50°C), 11.8 (60°C), 9.45 (70°C), 7.74 (80°C).In a reaction vessel diethyl ether, Et ₂ O (10 mL), cooled to -78 ° C and degassed. Subsequently, C ₂ F ₅ H (720 mg, 6.00 mmol) is condensed in and n-BuLi (2.5 M in hexane, 2.0 mL, 5.0 mmol) is added within 5 min. Thereafter, a solution of BH ₃ · THF (≈ 2.5 ± 0.1 M in THF, 4.0 mL, 10.0 mmol) is added dropwise over 20 min. The reaction mixture is slowly warmed to -20 ° C in the cold bath and then added to a solution of K ₂ CO ₃ (3 g) in H ₂ O (10 mL). The two-phase system is extracted with Et ₂ O (15 x 6 mL) and a 1: 1 mixture of THF and Et ₂ O (2 x 10 mL). Then, the organic phase with an aqueous solution of 1-ethyl-3-methylimidazolium chloride (EMIM Cl solution, ≈ 0.71 M, 7.0 mL, 5 mmol) and stirred for 1 hour at room temperature. The organic phase is removed and the aqueous phase extracted with CH ₂ Cl ₂ (5 x 6 mL). The combined organic phases are dried with MgSO ₄ and then filtered. The solvent is removed in a fine vacuum and a yellowish, clear liquid is obtained.
Yield of [EMIM] [C ₂ F ₅ BH ₃ ]: 0.821 g (3.36 mmol, 67% with respect to the amount of n-BuLi used).

¹ H-NMR (500.13 MHz, acetone-d ₆ ) δ, ppm: 8.96 (s, 1H, CH, H ³ ), 7.70 (dd, ³ J ( ¹ H, ¹ H) ≈ ³ J ( ¹ H, ¹ H) ≈ 1.80 Hz, 1H, CH, H ⁴ ), 7.62 (dd, ³ J ( ¹ H, ¹ H) ≈ ³ J ( ¹ H, ¹ H) ≈ 1.80 Hz, 1H, CH, H ⁴ ), 4.34 (q, ³ J ⁽¹ H, ¹ H) = 7.25 Hz, 2H, CH _2, H ^2), 3.99 (s, 3H, CH _3, H ^5), 1:53 (t, ³ J ⁽¹ H, ¹ H ) = 7.32 Hz, 3H, CH ₃ , H ¹ ), 0.94-0.25 (m, 3H, ¹⁰ BH ₃ ), 0.65 (qtq, ¹ J ( ¹¹ B, ¹ H) = 84.63 Hz, ³ J ( ¹⁹ F, ¹ H) = 27.35 Hz, ⁴ J ( ¹⁹ F, ¹ H) = 3.75 Hz, 3H, ¹¹ BH ₃ ).
¹ H { ¹⁰ B} NMR (500.13 MHz, acetone-d ₆ ) δ, ppm: 8.96 (s, 1H, CH, H ³ ), 7.69 (dd, ³ J ( ¹ H, ¹ H) ≈ ³ J ( ¹ H, ¹ H) ≈ 1.70 Hz, 1H, CH, H ⁴ ), 7.62 (dd, ³ J ( ¹ H, ¹ H) ≈ ³ J ( ¹ H, ¹ H) ≈ 1.55 Hz, 1H, CH, H ⁴ ), 4.34 (q, ³ J ( ¹ H, ¹ H) = 7.34 Hz, 2H, CH ₂ , H ² ), 3.99 (s, 3H, CH ₃ , H ⁵ ), 1.53 (t, ³ J ( ¹ H, ¹ H) = 7.37 Hz, 3H, CH ₃ , H ¹ ), 0.60 (tq, ³ J ( ¹⁹ F, ¹ H) = 27.41 Hz, ⁴ J ( ¹⁹ F, ¹ H) = 3.78 Hz, 3H, BH ₃ ), 0.57 (qtq, ¹ J ( ¹¹ B, ¹ H) = 84.72 Hz, ³ J ( ¹⁹ F, ¹ H) = 27.35 Hz, ⁴ J ( ¹⁹ F, ¹ H) = 3.63 Hz, 3H, BH ₃ ).
¹ H { ¹¹ B} NMR (500.13 MHz, acetone-d ₆ ) δ, ppm: 8.96 (s, 1H, CH, H ³ ), 7.70 (dd, ³ J ( ¹ H, ¹ H) ≈ ³ J ( ¹ H, ¹ H) ≈ 1.78 Hz, 1H, CH, H ⁴ ), 7.62 (dd, ³ J ( ¹ H, ¹ H) ≈ ³ J ( ¹ H, ¹ H) ≈ 1.78 Hz, 1H, CH, H ^4), 4:34 (q, ³ J ⁽¹ H, ¹ H) = 7.32 Hz, 2H, CH _2, H ^2), 3.99 (s, 3H, CH _3, H ^5), 1:53 (t, ³ J ⁽¹ H, ¹ H) = 7.33 Hz, 3H, CH _3, H ^1), 0.83-0.35 (m, 3H, ¹⁰ BH _3), 0:57 (tq, ³ J ⁽¹⁹ F, ¹ H) = 27.40 Hz, ⁴ J ( ¹⁹ F, ¹ H) = 3.77 Hz, 3H, ¹¹ BH ₃ ).
¹⁰ B { ¹ H} NMR (53.73 MHz, acetone-d ₆ ) δ, ppm: -33.0 (t, ² J ( ¹⁹ F, ¹⁰ B) = 6.1 Hz).
¹¹ B-NMR (160.46 MHz, acetone-d ₆ ) δ, ppm: -32.9 (qt, ¹ J ( ¹¹ B, ¹ H) = 84.6 Hz, ² J ( ¹⁹ F, ¹¹ B) = 18.5 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz, acetone-d ₆ ) δ, ppm: -32.9 (t, J ( ¹⁹ F, ¹¹ B) = 18.3 Hz).
¹³ C { ¹ H} NMR (125.76 MHz, acetone-d ₆ ) δ, ppm: 136.9 (s, 1C, CH, CH ³ ), 133.8 (tqq, ¹ J ( ¹⁹ F, ¹³ C) = 242.2 Hz, ² J ⁽¹⁹ F, ¹¹ B) = 52.8 Hz, ² J ⁽¹⁹ F, ¹³ C) = 35.2 Hz, 1C, CF _2), 124.4 (s, 1C, CH, CH ⁴⁾ 123.7 (QTQ, ¹ J ( ¹⁹ F, ¹³ C) = 286.0 Hz, ² J ( ¹⁹ F, ¹³ C) = 35.3 Hz, ³ J ( ¹⁹ F, ¹¹ B) = 3.3 Hz, 1C, CF ₃ ), 122.8 (s, 1C, CH, CH ⁴ ), 45.5 (s, 1C, CH ₂ , CH ² ), 36.5 (s, 1C, CH ₃ , CH ⁵ ), 15.4 (s, 1C, CH ₃ , CH ¹ ).
¹⁹ F NMR (188.12 MHz, _acetone-d6) δ, ppm: -84.6 (s, 3F, CF _3), -111.1 (qq, ² J ⁽¹⁹ F, ¹¹ B) = 18.5 Hz, J ^{2 (19} F, ¹ H) = 27.4 Hz, 2F, CF ₂ ).
¹⁹ F { ¹ H} NMR (188.12 MHz, acetone-d ₆ ) δ, ppm: -84.6 (s, 3F, CF ₃ ), -111.1 (q, ² J ( ¹⁹ F, ¹¹ B) = 18.3 Hz, 2F, CF ₂ ).

Elemental analysis,%: found (calculated): C 39.84 (39.38), H 5.84 (5.78), N 11.90 (11.48).

Dynamic Viscosity, η, mPa · s: 37.6 (20 ° C), 26.7 (30 ° C), 19.7 (40 ° C), 15.0 (50 ° C), 11.8 (60 ° C), 9.45 (70 ° C) , 7.74 (80 ° C).

Example 2: Synthesis of tetraphenylphosphonium 2,2,2-trifluoroethyl dicyanohydridoborate; [Ph ₄ P] [CF ₃ CH ₂ BH (CN) ₂ ]

Tetrabutylammonium pentafluoroethyl trihydridoborate ([TBA] [C ₂ F ₅ BH ₃ ], 20.0 g, 52.9 mmol) is introduced into an autoclave and treated with trimethylsilyl cyanide, (CH ₃ ) ₃ SiCN (63.4 g, 0.64 mol, 80 mL). Subsequently, the reaction mixture is heated for 17 hours to 200 ° C (temperature of the heating hood), whereby a pressure of 7 bar is reached. Thereafter, all volatiles are condensed off. The residue is taken up in acetone, insoluble constituents are filtered off and the solvent is removed. The residue is dried in a fine vacuum (3 × 10 ^-3 mbar). Thereafter, the residue is suspended in 20% HCl (150 mL) and extracted with diethyl ether (3 × 100 mL). The combined organic phases are combined with water (150 mL) and Et ₂ O removed. The aqueous phase is filtered through Celite. Thereafter, a solution of tetraphenylphosphonium bromide, ([Ph ₄ P] Br, 6.20 g, 14.8 mmol in 300 mL H ₂ O) is slowly added and the precipitated pale yellow solid is filtered off. The product is dried in a fine vacuum (1 × 10 ^-3 mbar).
Yield of [Ph ₄ P] [CF ₃ CH ₂ BH (CN) ₂ ]: 5.30 g (10.7 mmol, 20% with respect to the amount of [TBA] [C ₂ F ₅ BH ₃ ] used).

NMR data for [Ph ₄ P] [CF ₃ CH ₂ BH (CN) ₂ ] in acetone-d6:
¹ H-NMR (500.13 MHz) δ, ppm: 8.06-7.99 (m, 4H, PPh ₄ ), 7.92-7.85 (m, 16H, PPh ₄ ), 1.60 (qt, 1H, BH (CN) ₂ , ¹ J ( ¹ H, ¹¹ B) = 93.8 Hz, ³ J ( ¹ H, ¹ H) = 6.0 Hz), 1.29-1.15 (m, 2C, CH ₂ ).
¹ H { ¹¹ B} NMR (500.13 MHz) δ, ppm: 8.06-7.99 (m, 4H, PPh ₄ ), 7.92-7.85 (m, 16H, PPh ₄ ), 1.60 (t, 1H, BH (CN) ₂ , ³ J ( ¹ H, ¹ H) = 6.0 Hz), 1.22 (qd, 2H, CH ₂ , ³ J ( ¹ H, ¹⁹ F) = 14.0 Hz, ³ J ( ¹ H, ¹ H) = 6.0 Hz ).
¹ H { ³¹ P} NMR (500.13 MHz) δ, ppm: 8.06-7.99 (m, 4H, PPh ₄ ), 7.92-7.85 (m, 16H, PPh ₄ ), 1.60 (qt, 1H, BH (CN) ₂ , ¹ J ( ¹ H, ¹¹ B) = 93.8 Hz, ³ J ( ¹ H, ¹ H) = 6.0 Hz), 1.29-1.15 (m, 2C, CH ₂ ).
³¹ P-NMR (202.45 MHz) δ, ppm: 23.0 (m).
³¹ P { ¹ H} NMR (202.45 MHz) δ, ppm: 23.0 (s).
¹¹ B NMR (160.46 MHz) δ, ppm: -34.8 (d, ¹ J ( ¹¹ B, ¹ H) = 93.5 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz) δ, ppm: -34.8 (q, ³ J ( ¹¹ B, ¹⁹ F) = 5.8 Hz).
¹¹ B { ¹⁹ F} NMR (160.46 MHz) δ, ppm: -35.8 (dt, ¹ J ( ¹¹ B, ¹ H) = 93.7 Hz, ² J ( ¹¹ B, ¹ H) = 4.9 Hz).
¹⁹ F-NMR (470.59 MHz) δ, ppm: -58.8 (tq, ³ J ( ¹⁹ F, ¹ H) = 14.0 Hz, ³ J ( ¹⁹ F, ¹¹ B) = 5.1 Hz).
¹⁹ F { ¹¹ B} NMR (470.59 MHz) δ, ppm: -58.8 (t, ³ J ( ¹⁹ F, ¹ H) = 14.0 Hz).
¹³ C { ¹ H} NMR (125.75 MHz) δ, ppm: 135.5 (d, ³ J ( ³¹ P, ¹³ C) = 3.15 Hz, 4C), 134.8 (d, ² J ( ³¹ P, ¹³ C) = 10.4 Hz, 8C), 130.5 (d, ³ J ( ³¹ P, ¹³ C) = 12.9 Hz, 8C), 118.1 (d, ¹ J ( ³¹ P, ¹³ C) = 89.5 Hz), 23.3 (qq, CH ₂ , 1C, ¹ J ⁽¹³ C, ¹¹ B) = 43.0 Hz, ² J ⁽¹³ C, ¹⁹ F) = 25.4 Hz).
¹³ C { ¹¹ B, ¹ H} NMR (75.48 MHz) δ, ppm: 135.5 (d, ³ J ( ³¹ P, ¹³ C) = 3.15 Hz, 4C), 134.8 (d, ² J ( ³¹ P, ¹³ C) = 10.4 Hz, 8C) 133.5 (s, 2C, CN), 130.8 (q, 1C, _CF3, ¹ J ⁽¹³ C, ¹⁹ F) = 275.0 Hz), 130.5 (d, ³ J ⁽³¹ P , ¹³ C) = 12.9 Hz, 8C), 118.1 (d, ¹ J ( ³¹ P, ¹³ C) = 89.5 Hz), 23.3 (q, CH ₂ , ¹ C, ² J ( ¹³ C, ¹⁹ F) = 25.2 Hz ).

IR spectroscopy [υ~]: 2387 cm ^-1 (BH).

Example 3: Synthesis of potassium 2,2,2-trifluoroethyl tricyanoborate, K [CF ₃ CH ₂ B (CN) ₃ ]

[TBA] [C ₂ F ₅ BH ₃ ] (2.00 g, 5.30 mmol) is placed in an autoclave and treated with trimethylsilyl cyanide (63.4 g, 0.63 mol, 80.0 ml). Subsequently, the reaction mixture is heated for 30 h at 200 ° C (temperature of the heating hood), wherein a pressure of 2 bar sets. Thereafter, all volatiles are condensed off. The residue is dried in a fine vacuum (1 × 10 ^-3 mbar) and then combined with 20% HCl (100 ml) and extracted with Et ₂ O (3 × 100 ml). Thereafter, the combined diethyl ether phases with an aqueous K ₂ CO ₃ solution and the organic phase rotary evaporator removed by means of a. Oily droplets form on the aqueous phase but do not contain any product and are therefore removed. Thereafter, an extraction of the aqueous phase with THF (3 × 50.0 ml). The combined organic phases are dried with K ₂ CO ₃ and filtered off. The filtrate is concentrated using a rotary evaporator and the product is precipitated by addition of CH ₂ Cl ₂ (100 ml), filtered off and dried in a fine vacuum (1 × 10 ^-3 mbar).
Yield: 200 mg (17% of a light yellow solid, 0.94 mmol).
Purity: 97% ( ¹¹ B NMR spectroscopy).

Elemental analysis [%]: found (calculated) for KC ₅ H ₂ BF ₃ N ₃ :
C 28.32 (28.46), H 0.57 (0.96), N 20.17 (19.92).

NMR data for K [CF ₃ CH ₂ B (CN) ₃ ] in acetone-d6:
¹ H-NMR (500.13 MHz) δ, ppm: 1.47 (qq, 2H, CH ₂ , ² J ( ¹ H, ¹¹ B) = 4.7 Hz, ³ J ( ¹ H, ¹⁹ F) = 13.5 Hz).
¹ H { ¹¹ B} NMR (500.13 MHz) δ, ppm: 1.47 (q, 2H, CH ₂ , ³ J ( ¹ H, ¹¹ B) = 13.1 Hz).
¹ H { ¹⁹ F} NMR (199.92 MHz) δ, ppm: 1.42 (m).
¹¹ B NMR (160.46 MHz) δ, ppm: -33.4 (tq, ² J ( ¹¹ B, ¹ H) = 5.7 Hz, ³ J ( ¹¹ B, ¹⁹ F) = 5.8 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz) δ, ppm: -33.4 (q, ³ J ( ¹¹ B, ¹⁹ F) = 5.8 Hz).
¹¹ B { ¹⁹ F} NMR (160.46 MHz) δ, ppm: -34.4 (t, ² J ( ¹¹ B, ¹ H) = 5.3 Hz).
¹⁹ F NMR (470.59 MHz) δ, ppm: -58.0 (tq, ³ J ⁽¹⁹ F, ¹ H) = 13.7 Hz, ³ J ⁽¹⁹ F, ¹¹ B) = 4.6 Hz).
¹⁹ F { ¹ H} NMR (188.11 MHz) δ, ppm: -58.0 (q, CF ₃ , ³ J ( ¹⁹ F, ¹¹ B) = 6.6 Hz).
¹⁹ F { ¹¹ B} NMR (470.59 MHz) δ, ppm: -58.0 (t, ³ J ( ¹⁹ F, ¹ H) = 13.1 Hz).
¹³ C { ¹ H} NMR (125.75 MHz) δ, ppm: 25.4 (qq, 1C, CH ₂ , ¹ J ( ¹³ C, ¹¹ B) = 44.5 Hz, ² J ( ¹³ C, ¹⁹ F = 25.5 Hz) , 128.0 (q, CN, ¹ J ( ¹³ C, ¹¹ B) = 65.7 Hz), 129.3 (q, CF ₃ , ¹ J ( ¹³ C, ¹⁹ F) = 275.0 Hz).
¹³ C { ¹¹ B, ¹ H} NMR (75.48 MHz) δ, ppm: 24.9 (q, CH ₂ , ² J ( ¹³ C, ¹⁹ F) = 26.1 Hz), 127.5 (s, CN), 128.8 (q , CF ₃ , ¹ J ( ¹³ C, ¹⁹ F) = 275.5 Hz).
¹³ C { ¹¹ B} NMR (75.48 MHz) δ, ppm: 24.9 (tq, CH ₂ , ¹ J ( ¹³ C, ¹ H) = 122.8 Hz, ² J ( ¹³ C, ¹⁹ F) = 26.2 Hz), 127.5 (t, CN, ³ J ( ¹³ C, ¹ H) = 4.7 Hz), 128.8 (qt, CF ₃ , ¹ J ( ¹³ C, ¹⁹ F) = 275.5 Hz, ² J ( ¹³ C, ¹ H) = 7.5 Hz).

IR spectroscopy [ν ~]: 2224 cm ^-1 (CN).
Raman spectroscopy [υ ~]: 2221 cm ^-1 (CN).

MALDI-MS m / z for C ₅ H ₂ BF ₃ N ₃ :
calculated: 172.03 (100%), 171.03 (24.8%), 173.03 (5.4%), 172.04 (1.3%)
found: 171.8 (100%), 170.8 (46%), 172.8 (11%), 172.0 (2%).

Example 4: Synthesis of tetraethylammonium pentafluoroethyldicyanohydridoborate; [TEA] [C ₂ F ₅ BH (CN) ₂ ]

K [C ₂ F ₅ BF (CN) ₂ ] (1.00 g, 4.20 mmol) is suspended with KH (1.66 g, 41.6 mmol) and LiCl (1.00 g, 23.5 mmol) in tetrahydrofuran, THF (20 mL). Thereafter, the reaction mixture is stirred for 64 hours at 80 ° C (bath temperature), wherein it is aerated every 24 hours due to the H ₂ -Dikerviklung. Subsequently, additional KH (0.4 g, 10.0 mmol) and LiCl (0.5 g, 11.7 mmol) are added and stirred at 80 ° C for a further 44 hours. Then, the reaction mixture is filtered inert, the filtrate with deionized water (10.0 mL) and the THF is removed by distillation. Subsequently, a solution of tetraethylammonium bromide ([TEA] Br; 874 mg, 4.20 mmol in 20 mL H ₂ O) is added dropwise. The aqueous solution is extracted with CH ₂ Cl ₂ (5 x 50 mL) and the solvent of the combined organic phases is removed. Subsequently, the resulting solid is dried in a fine vacuum (1 × 10 ^-3 mbar).
Yield of [TEA] [C ₂ F ₅ BH (CN) ₂ ]: 270 mg (0.86 mmol, 20% with respect to the amount of K [C ₂ F ₅ BF (CN) ₂ ] used).

NMR data for [TEA] [C ₂ F ₅ BH (CN) ₂ ] in acetone-d6:
¹ H-NMR (500.13 MHz) δ, ppm: 3.5 (q, 2H, CH ₂ , ³ J ( ¹ H, ¹ H) = 7.3 Hz), 1.2 (tt, 3H, CH ₃ , ³ J ( ¹ H, ¹ H) = 7.3 Hz, ³ J ( ¹ H, ¹⁴ N) = 1.9 Hz), 1.75 (qt, ¹ J ( ¹¹ B, ¹ H) = 95.6 Hz, ³ J ( ¹⁹ F, ¹ H) = 19.4 Hz ).
¹ H { ¹¹ B} NMR (500.13 MHz) δ, ppm: 3.5 (q, 2H, CH ₂ , ³ J ( ¹ H, ¹ H) = 7.3 Hz), 1.2 (t, 3H, CH ₃ , ³ J ( ¹ H, ¹ H) = 7.3 Hz, ³ J ( ¹ H, ¹⁴ N) = 1.9 Hz), 1.73 (tq, ³ J ( ¹ H, ¹⁹ F) = 19.3 Hz, ⁴ J ( ¹ H, ¹⁹ F ) = 2.2 Hz).
¹¹ B NMR (160.46 MHz) δ, ppm: -33.0 (dt, ¹ J ( ¹¹ B, ¹ H) = 95.1 Hz, ³ J ( ¹¹ B, ¹⁹ F) = 22.6 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz) δ, ppm: -33.0 (t, ³ J ( ¹¹ B, ¹⁹ F) = 22.6 Hz).
¹⁹ F-NMR (470.59 MHz) δ, ppm: -84.0 (s, 3F, CF ₃ ), -122.3 (dq, ³ J ( ¹⁹ F, ¹ H) = 22.7 Hz, ² J ( ¹⁹ F, ¹¹ B) = 22.8 Hz).
¹³ C { ¹ H} NMR (125.75 MHz) δ, ppm: 6.7 (s, 4C, CH ₃ ), 52.1 (t, 4C, CH ₂ , ¹ J ( ¹³ C, ¹⁴ N) = 3.1 Hz), 123.8 (qt, CF ₃ , ¹ J ( ¹³ C, ¹⁹ F) = 283.7 Hz, ² J ( ¹³ C, ¹⁹ F) = 35.7 Hz), 128.1 (qt, CN, ¹ J ( ¹³ C, ¹¹ B) = 63.8 Hz, ³ J ( ¹³ C, ¹⁹ F) = 6.0 Hz).
¹³ C { ¹¹ B, ¹ H} NMR (75.48 MHz) δ, ppm: 6.7 (s, 4C, CH ₃ ), 52.1 (t, 4C, CH ₂ , ¹ J ( ¹³ C, ¹⁴ N) = 3.1 Hz ), 121.5 (qt, CF ₃ , ¹ J ( ¹³ C, ¹⁹ F) = 286.0 Hz, ² J ( ¹³ C, ¹⁹ F) = 32.9 Hz), 121.7 (tq, CF ₂ , ¹ J ( ¹³ C, ¹⁹ F) = 257.0 Hz, ² J ( ¹³ C, ¹⁹ F) = 36.2 Hz), 128.1 (t, CN, ³ J ( ¹³ C, ¹⁹ F) = 6.8 Hz).
¹³ C { ¹¹ B} NMR (75.48 MHz) δ, ppm: 6.7 (qt, 4C, CH ₃ , ¹ J ( ¹³ C, ¹ H) = 128.7 Hz, ² J ( ¹³ C, ¹ H) = 3.5 Hz ), 52.1 (t, 4C, CH ₂ , ¹ J ( ¹³ C, ¹ H) = 144.7 Hz), 121.5 (qt, CF ₃ , ¹ J ( ¹³ C, ¹⁹ F) = 284.9 Hz, ² J ( ¹³ C , ¹⁹ F) = 33.1 Hz), 121.7 (tqd, CF ₂ , ¹ J ( ¹³ C, ¹⁹ F) = 257.3 Hz, ² J ( ¹³ C, ¹⁹ F) = 36.3 Hz), ² J ( ¹³ C, ¹ H) = 7.1 Hz), 128.1 (dt, CN, ² J ( ¹³ C, ¹ H) = 9.9 Hz, ³ J ( ¹³ C, ¹⁹ F) = 7.2 Hz).

Raman spectroscopy [ν ~]: 2208 cm ^-1 (CN).
IR spectroscopy [υ~]: 2415 cm ^-1 , 2328 cm ^-1 (BH).

Example 5: Synthesis of Tetrabutylammonium Trifluoromethyldicyanohydridoborate, [TBA] [CF ₃ BH (CN) ₂ ]

K [CF ₃ BF (CN) ₂ ] (400 mg, 2.1 mmol) is taken up together with KH (400 mg, 9.97 mmol) and LiBr (200 mg, 2.33 mmol) in THF (10 mL). The suspension is stirred for 5 days at 66 ° C and then at 80 ° C for 5 days. After 2 days at 66 ° C. and after one day at 80 ° C. (bath temperature), in each case KH (100 mg, 2.49 mmol) and LiBr (1.16 mmol) are added. During the conversion, H ₂ evolution takes place. Then all volatiles are removed in vacuo and the residue extracted with THF (10 mL), filtered and concentrated in vacuo. The resulting solid is dissolved in H ₂ O (5 mL) and treated with tetrabutylammonium bromide, [n -Bu ₄ N] Br (600 mg, 1.86 mmol). The clear solution is extracted with CH ₂ Cl ₂ (2 × 15 mL) and the combined organic phases are then concentrated in vacuo to dryness. The resulting product [n-Bu ₄ N] [CF ₃ BH (CN) ₂ ] is dried in a fine vacuum (3 × 10 ^-3 mbar).
Yield: 135 mg (0.35 mmol, corresponding to 17% based on the borate used).
Elemental analysis: found (calculated): C 42.34 (41.89), H 6.19 (6.25), N 10.62 (10.81).
T _calc .: 225 ° C (T _onset ).

¹⁹ F-NMR (188.09 MHz, acetone-d6) δ, ppm: -61.2 (qd, ² J ( ¹⁹ F, ¹¹ B) = 34.7 Hz, ³ J ( ¹⁹ F, ¹ H) = 11.5 Hz, 3F, CF ₃ ).
¹⁹ F { ¹ H} NMR (188.09 MHz, acetone-d6) δ, ppm: -61.2 (q, ² J ( ¹⁹ F, ¹¹ B) = 34.7 Hz, 3F, CF ₃ ).
¹ H-NMR (500.13 MHz, acetone-d6) δ, ppm: 3.44-3.41 (m, 8H, NCH ₂ ), 1.82-1.76 (m, 8H, CH ₂ ), 1.42 (sx, 8H, CH ₂ , ³ J ( ¹ H, ¹ H) = 7.5 Hz), 0.98 (t, 12H, CH ₃ , ³ J ( ¹ H, ¹ H) = 7.4 Hz), 0.69 (qq, 1H, BH, ³ J ( ¹⁹ F, ¹ H) = 11.5 Hz, ¹ J ( ¹¹ B, ¹ H) ≈ 96 Hz).
¹ H { ¹¹ B} NMR (500.13 MHz, acetone-d6) δ, ppm: 3.44-3.41 (m, 8H, NCH ₂ ), 1.82-1.76 (m, 8H, CH ₂ ), 1.42 (sx, 8H, CH ₂ , ³ J ( ¹ H, ¹ H) = 7.5 Hz), 0.98 (t, 12H, CH ₃ , ³ J ( ¹ H, ¹ H) = 7.4 Hz), 0.69 (q, 1H, BH, ³ J ( ¹⁹ F, ¹ H) = 11.5 Hz).
¹¹ B-NMR (160.46 MHz, acetone-d6) δ, ppm: -33.7 (dq, ¹ J ( ¹¹ B, ¹ H) = 95.3 Hz, ² J ( ¹¹ B, ¹⁹ F) = 35.0 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz, acetone-d6) δ, ppm: -33.7 (q, ² J ( ¹¹ B, ¹⁹ F) = 35.0 Hz).
¹³ C { ¹ H} NMR (125.77 MHz, acetone-d6) δ, ppm: ≈136 (m, 1C, CF ₃ ), 129.3 (q, ¹ J ( ¹³ C, ¹ H) = 63.2 Hz, 2C, CN), 59.3 (t, ¹ J ( ¹³ C, ¹⁴ N) = 2.8 Hz), 24.4 (s, 4C), 20.3 (s, 4C), 13.8 (s, 4C).

Example 6: Synthesis of tetrabutylammonium pentafluoroethyl trihydridoborate, [TBA] [C ₂ F ₅ BH ₃ ]

A)

First, a BH ₃ · THF solution is prepared. To this is added Na [BH ₄ ] (7.56 g, 200 mmol) and suspended in tetrahydrofuran, THF (200 ml). Subsequently, trimethylsilyl chloride, TMSCl (20.6 g, 190 mmol, 24.2 ml) is added. The reaction mixture is stirred for 15 hours at room temperature. In parallel, THF (200 ml) is placed in a reaction vessel, cooled to -78 ° C and degassed. C ₂ F ₅ H (190 mmol, 22.8 g) is condensed in and n-BuLi (2.5 M solution in hexane, 185 mmol, 74.0 ml) is slowly added dropwise over 60 min with vigorous stirring. The previously prepared BH ₃ · THF solution is cooled to -78 ° C and added to the reaction solution. The reaction mixture is then slowly warmed to room temperature and added with stirring to a solution of K ₂ CO ₃ (13.8 g, 99 mmol) in 200 ml of deionized water. After that, most of the THF is distilled off. To the aqueous phase is slowly added a terabutylammonium bromide solution ([TBA] Br solution, 189 mmol, 61.0 g in 100 mL deionized H ₂ O). The resulting solid is filtered off and dried in a fine vacuum (1 × 10 ^-3 mbar).
Yield of [TBA] [C ₂ F ₅ BH ₃ ]: 41.96 g (112 mmol, 60% based on the amount of n-BuLi used).
Purity: 99% (confirmed by ¹⁹ F NMR spectroscopy).

¹¹ B NMR (160.46 MHz, acetone-d6), δ, ppm: -33.3 (qt, ¹ J ( ¹¹ B, ¹ H) = 84.7 Hz, ² J ( ¹¹ B, ¹⁹ F) = 18.3 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz, acetone-d6), δ, ppm: -33.3 (t, ² J ( ¹¹ B, ¹⁹ F) = 18.3 Hz).
¹⁹ F NMR (470.59 MHz, acetone-d6), δ, ppm: -84.4 (s, 3F, CF _3), -110.9 (qq, ² J ⁽¹⁹ F, ¹¹ B) = 18.3 Hz, ³ J ⁽¹⁹ F, ¹ H) = 27.8 Hz, 2F, CF ₂ ).
¹⁹ F { ¹ H} NMR (376.75 MHz, acetone-d6), δ, ppm: -84.4 (s, 3F, CF ₃ ), -110.9 (q, ² J ( ¹⁹ F, ¹¹ B) = 18.3 Hz, 2F, CF ₂ ).
¹ H-NMR (500.13 MHz, acetone-d6), δ, ppm: 3.46-3.30 (m, 8H, NCH ₂ ), 1.87-1.64 (qi, 8H, CH ₂ , ³ J ( ¹ H, ¹ H) 7.9 Hz), 1.38 (sx, 8H, CH ₂ , ³ J ( ¹ H, ¹ H) = 7.5 Hz), 0.92 (t, 12H, CH-, ³ J ( ¹ H, ¹ H) = 7.4 Hz), 12:41 (tq, 3H, BH _3, ³ J ⁽¹⁹ F, ¹ H) = 27.8 Hz, ⁴ J ⁽¹⁹ F, ¹ H) = 3.95 Hz).
¹³ C { ¹ H} NMR (125.76 MHz, acetone-d ₆ ), δ, ppm: δ = 59.4 (t, ¹ J ( ¹⁴ N, ¹³ C) = 2.1 Hz 4C, NCH ₂ ), 24.4 (s, 4C, CH ₂ ), 20.4 (s, 4C, CH ₂ ), 13.8 (s, 4C, CH ₃ ).

B)

In the first step, a BH ₃ -THF solution is produced. For this, Na [BH ₄ ] (2.70 g, 70.0 mmol) is initially charged and suspended in THF (150 ml). Subsequently, trimethylsilyl chloride, TMSCl (8.39 ml, 7.20 g, 66.0 mmol) was added dropwise and the reaction mixture was stirred at RT for 20 h. The suspension is then filtered inert. In the second step, Et ₂ O (100 ml) is cooled to -78 ° C and then degassed. Thereafter, C ₂ F ₅ H (8.00 g, 66.0 mmol) is condensed and cooled to 4 ° C n-BuLi (2.5 M in hexane, 24.0 ml, 60.0 mmol) slowly added dropwise with vigorous stirring over 30 min, with a slight yellow-brown color the reaction solution occurs. The BH ₃ · THF solution from step 1 is also cooled to -78 ° C and added to the C ₂ F ₅ Li solution prepared in the 2nd step. Thereafter, the reaction mixture is slowly warmed to RT and added to a solution of K ₂ CO ₃ (5.00 g, 36.1 mmol) in H ₂ O (100 ml) and stirred at RT for 15 h. For further work-up, the THF / Et ₂ O mixture is removed by means of a rotary evaporator and a tetrabutylammonium hydroxide, [TBA] OH solution (40% by weight in H ₂ O, 39 ml) is added slowly to the remaining aqueous phase. The resulting colorless solid is filtered off and dried in a fine vacuum (1 × 10 ^-3 mbar).
Yield: 12.1 g (32.2 mmol, 53% based on the amount of n-BuLi used) of a colorless solid.
Purity: 98% ( ¹¹ B NMR spectroscopy).

The NMR spectra are identical to the spectra described in Example 6, A).

C)

First, Et ₂ O (5 mL) is cooled to -78 ° C and degassed. Now, C ₂ F ₅ H (363 mg, 3.03 mmol) is condensed in, n-BuLi (2.5 M in hexane, 1.10 mL, 2.75 mmol) is added dropwise, a solution of BH ₃ .THF (~ 1.8 ± 0.1 M in THF, 3.0 mL, 5.4 mmol) was added dropwise over 5 min and the brownish solution was slowly warmed to RT in a cold bath. Subsequently, the reaction mixture is added to a solution of K ₂ CO ₃ (1 g) in H ₂ O (5 mL) and stirred at RT for 30 min. The aqueous phase is separated and extracted with a 1: 1 mixture of THF and Et ₂ O (5 x 5 mL). The organic phase is treated with a solution of tetrabutylammonium bromide (887 mg, 2.75 mmol) in H ₂ O (5 mL) and stirred at RT over the weekend. The remaining aqueous phase is extracted with CH ₂ Cl ₂ (4 x 6 mL), the CH ₂ Cl ₂ phases combined, dried with MgSO ₄ and filtered. The solvent is removed with a rotary evaporator at 35 ° C and then in a fine vacuum. The residue is taken up in a few milliliters of acetone and added dropwise to an excess of H ₂ O. After the suspension is stirred overnight, the solid is filtered off, washed with a few milliliters of Et ₂ O and dried in a vacuum desiccator.

Yield: 0.60 g (1.59 mmol, 58% based on the amount of n-BuLi used).

Elemental analysis [%]: found (calculated): C 58.15 (57.60), H 10.66 (10.47), N 3.91 (3.73).

The NMR spectra are identical to the spectra described in Example 6 A).

Example 7: Synthesis of tetraphenylphosphonium pentafluoroethyl trihydridoborate, [Ph ₄ P] [C ₂ F ₅ BH ₃ ]

A solution of BH ₃ .THF (~1.8. + -. 0.1 M in THF, 2.3 mL, 4.1 mmol) is initially charged, then cooled to -78.degree. C. and degassed. Subsequently, C ₂ F ₅ H (132 mg, 1.10 mmol) is condensed in, n-BuLi (2.5 M in hexane, 0.4 mL, 1 mmol) is added dropwise over 15 min. The slightly brownish solution is slowly warmed to RT in a cold bath and stirred overnight at RT. The resulting colorless solution is treated with a solution of K ₂ CO ₃ (1 g) in H ₂ O (10 mL) and stirred for 30 min. Subsequently, a solution of [Ph ₄ P] Br (343 mg, 0.818 mmol) in H ₂ O (5 mL) is added and stirred at RT overnight. The remaining aqueous solution is extracted with CH ₂ Cl ₂ (3 × 10 mL) and the CH ₂ Cl ₂ phases combined. The combined organic phases are dried with MgSO ₄ , then filtered and the solvent removed in vacuo. The residue is treated with H ₂ O (10 mL) and stirred at RT overnight. The suspension is filtered and the resulting colorless solid dried in a vacuum desiccator.

Yield: 0.285 g (0.604 mmol, 60% based on the amount of n-BuLi used, 15% based on the amount of BH ₃ · THF used).

Elemental analysis [%]: found (calculated): C 66.26 (66.13), H 4.98 (4.91).

¹ H-NMR (500.13 MHz, acetone-d ₆ ), δ, ppm: 8.06-7.94 (m, 4H, PPh ₄ ), 7.94-7.81 (m, 16H, PPh ₄ ), 1.07-0.37 (m, 3H, ¹⁰ BH ₃ ), 0.59 (qtq, ¹ J ( ¹¹ B, ¹ H) = 84.78 Hz, ³ J ( ¹⁹ F, ¹ H) = 27.97 Hz, ⁴ J ( ¹⁹ F, ¹ H) = 3.91 Hz, 3H, ¹¹ BH ₃ ).
¹ H { ¹¹ B} NMR (500.13 MHz, acetone-d ₆ ), δ, ppm: 8.07-7.94 (m, 4H, PPh ₄ ), 7.94-7.78 (m, 16H, PPh ₄ ), 0.97-0.46 ( m, 3H, ¹⁰ BH ₃ ), 0.71 (tq, ³ J ( ¹⁹ F, ¹ H) = 28.04 Hz, ⁴ J ( ¹⁹ F, ¹ H) = 3.94 Hz, 3H, ¹¹ BH ₃ ).
¹¹ B-NMR (160.46 MHz, acetone-d ₆ ), δ, ppm: -33.8 (qt, ¹ J ( ¹¹ B, ¹ H) = 84.9 Hz, ² J ( ¹⁹ F, ¹¹ B) = 18.2 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz, acetone-d ₆ ), δ, ppm: -33.3 (t, ² J ( ¹⁹ F, ¹¹ B) = 18.2 Hz) ppm.
¹³ C { ¹ H} NMR (125.76 MHz, acetone-d ₆ ), δ, ppm: 136.4 (d, ⁴ J ( ³¹ P, ¹³ C) = 3.2 Hz, 4C), 135.6 (d, (d, ² J ( ³¹ P, ¹³ C) = 10.4 Hz, 8C), 131.4 (d, ³ J ( ³¹ P, ¹³ C) = 12.9 Hz, 8C), 26.2 (d, ¹ J ( ³¹ P, ¹³ C) = 89.7 Hz, 4C).
³¹ P { ¹ H} NMR (202.46 MHz, acetone-d ₆ ), δ, ppm: 23.0 (m).
³¹ P { ³⁰ P} NMR (202.46 MHz, acetone-d ₆ ), δ, ppm: 23.0 (s).
¹⁹ F-NMR (188.12 MHz, acetone-d ₆ ), δ, ppm: -84.4 (q, ⁴ J ( ¹⁹ F, ¹ H) = 2.8 Hz 3F, CF ₃ ), -111.1 (qq, ² J ( ¹⁹ F, ¹¹ B) = 18.4 Hz, ² J ( ¹⁹ F, ¹ H) = 27.8 Hz, 2F, CF ₂ ).
¹⁹ F { ¹ H} NMR (188.12 MHz, acetone-d ₆ ), δ, ppm: -84.4 (s, 3F, CF ₃ ), -111.0 (q, ² J ( ¹⁹ F, ¹¹ B) = 18.2 Hz , 2F, CF ₂ ).

Example 8: Synthesis of N-butyl-N-methylpyrrolidinium pentafluoroethyl trihydridoborate, [BMPL] [C ₂ F ₅ BH ₃ ]

THF (1 mL) is cooled to -78 ° C and degassed. Subsequently, C ₂ F ₅ H (164 mg, 1.36 mmol) is condensed in, cooled nBuLi (-78 ° C, 2.5 M in hexane, 0.50 mL, 1.25 mmol) is added dropwise over 5 min and the solution is stirred for 10 min. Thereafter, a solution of BH ₃ .THF (~1.8. + -. 0.1 M in THF, 0.8 mL, 1.4 mmol) is added dropwise, and the brownish reaction mixture is slowly warmed to RT. Now, the reaction mixture is added to a solution of K ₂ CO ₃ (1 g) in H ₂ O (10 mL) and stirred at RT overnight. The remaining aqueous phase is treated with a solution of [BMPL] Cl (222 mg, 1.25 mmol) in H ₂ O (1 mL), stirred for a few minutes at RT and extracted with CH ₂ Cl ₂ (3 × 10 mL). The combined CH ₂ Cl ₂ phases are dried with MgSO ₄ and filtered. The solvent is largely removed with a rotary evaporator and the residue dried in a fine vacuum, whereupon a yellowish, clear liquid was obtained.
Yield: 0.132 g (0.480 mmol, 38% based on the amount of n-BuLi used).

¹ H-NMR (500.13 MHz, acetone-d ₆ ), δ, ppm: 3.73-3.62 (m, 4H, CH ₂ ), 3.54-3.49 (m, 2H, CH ₂ ), 3.20 (s, 3H, CH ₃ ), 2:32 to 2:24 (m, 4H, CH _2), 1.91-1.83 (m, 2H, CH _2), 1:46 to 1:37 (m, 2H, CH _2), 0.97 (t, ³ J ⁽¹ H, ¹ H ) = 7.40 Hz 3H, CH ₃ ), 0.91-0.25 (m, 3H, ¹⁰ BH ₃ ), 0.58 (qtq, ¹ J ( ¹¹ B, ¹ H) = 84.60 Hz, ³ J ( ¹⁹ F, ¹ H) 27.77 Hz, ⁴ J ( ¹⁹ F, ¹ H) = 3.84 Hz, 3H, ¹¹ BH ₃ ).
¹ H { ¹¹ B} NMR (500.13 MHz, acetone-d ₆ ), δ, ppm: 3.73-3.63 (m, 4H, CH ₂ ), 3.54-3.49 (m, 2H, CH ₂ ), 3.20 (s, 3H, CH _3), 2:32 to 2:24 (m, 4H, CH _2), 1.91-1.83 (m, 2H, CH _2), 1:46 to 1:37 (m, 2H, CH _2), 0.97 (t, ³ J ⁽¹ H, ¹ H) = 7.40 Hz 3H, CH ₃ ), 0.83-0.35 (m, 3H, ¹⁰ BH ₃ ), 0.58 (tq, ³ J ( ¹⁹ F, ¹ H) = 27.72 Hz, ⁴ J ( ¹⁹ F, ¹ H) = 3.85 Hz, 3H, ¹¹ BH ₃ ).
¹⁰ B-NMR (53.73 MHz, acetone-d ₆ ), δ, ppm: -33.8 (qt, ¹ J ( ¹⁰ B, ¹ H) = 28.3 Hz, ² J ( ¹⁹ F, ¹⁰ B) = 5.3 Hz).
¹⁰ B { ¹ H} NMR (53.73 MHz, acetone-d ₆ ), δ, ppm: -33.2 (t, ² J ( ¹⁹ F, ¹⁰ B) = 5.2 Hz).
¹¹ B-NMR (160.46 MHz, acetone-d ₆ ), δ, ppm: -33.7 (qt, ¹ J ( ¹¹ B, ¹ H) = 84.7 Hz, ² J ( ¹⁹ F, ¹¹ B) = 18.3 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz, acetone-d ₆ ), δ, ppm: -33.2 (t, ² J ( ¹⁹ F, ¹¹ B) = 18.3 Hz).
¹³ C { ¹ H} NMR (125.76 MHz, acetone-d ₆ ), δ, ppm: 65.1 (t, ¹ J ( ¹⁴ N, ¹³ C) = 3.2 Hz, 2C, CH ₂ ), 64.8 (t, ^{1 (14} N, ¹³ C) J = 3.0 Hz, 1C, CH _2), 48.9 (t, ¹ J ⁽¹⁴ N, ¹³ C) = 4.0 Hz, 1C, CH _3), 26.2 (s, 1C, CH ₂₎ , 22.2 (s, 2C, CH ₂ ), 20.3 (t, ¹ J ( ¹⁴ N, ¹³ C) = 1.5 Hz, 1C, CH ₂ ), 13.8 (s, 1C, CH ₃ ).
¹⁹ F-NMR (188.12 MHz, acetone-d ₆ ), δ, ppm: -84.4 (q, ⁴ J ( ¹⁹ F, ¹ H) = 2.6 Hz 3F, CF ₃ ), -111.0 (qq, ² J ( ¹⁹ F, ¹¹ B) = 18.4 Hz, ² J ( ¹⁹ F, ¹ H) = 27.6 Hz, 2F, CF ₂ ).
¹⁹ F { ¹ H} NMR (188.12 MHz, acetone-d ₆ ), δ, ppm: -84.4 (s, 3F, CF ₃ ), -111.0 (q, ² J ( ¹⁹ F, ¹¹ B) = 18.3 Hz , 2F, CF ₂ ).

Example 9: Synthesis of 1-ethyl-2,3-dimethylimidazolium pentafluoroethyl trihydridoborate, EDMIM [C ₂ F ₅ BH ₃ ]

C ₂ F ₅ H (562 mg, 4.68 mmol) is reacted in THF (6.0 mL) at -78 ° C with BuLi (2.5 M in hexanes, 1.0 mL, 2.5 mmol) and then BH ₃ .THF (0.74 M in THF, 3.4 mL, 2.5 mmol). The reaction mixture is warmed to RT and taken up with evolution of gas in H ₂ O (20 mL). The volatile constituents (THF, hexanes) are removed with a rotary evaporator and the residual aqueous phase is treated with [EDMIM] Cl (450 mg, 2.8 mmol). The solution is extracted with CH ₂ Cl ₂ (3 x 25 mL) and the combined organic phases are then concentrated in vacuo to dryness.
Yield: 260 mg (1.01 mmol, corresponding to 40% based on the n-BuLi used).

¹ H ^{11 B} NMR (199.9 MHz, acetone-d6), δ, ppm: 7.60 (d, ³ J ⁽¹ H, ¹ H) = 2.15 Hz, CH, 1H), 7:55 (d, ³ J ( ¹ H, ¹ H) = 2.15 Hz, CH, 1H), 4.29 (q, ³ J ( ¹ H, ¹ H) = 7.30 Hz, CH ₂ , 2H), 3.91 (s, CH ₃ , 3H), 2.74 ( s, CH ₃ , 3H), 1.46 (t, ³ J ( ¹ H, ¹ H) = 7.3 Hz, CH ₃ , 3H), 0.53 (tq, 3H, BH ₃ , ³ J ( ¹⁹ F, ¹ H) 27.9 Hz, ⁴ J ( ¹⁹ F, ¹ H) = 3.85 Hz).
¹ H-NMR (199.9 MHz, acetone-d6), δ, ppm: 7.60 (d, ³ J ( ¹ H, ¹ H) = 2.15 Hz, CH, 1H), 7.55 (d, ³ J ( ¹ H, ¹ H) = 2.15 Hz, CH, 1H), 4.29 (q, ³ J ⁽¹ H, ¹ H) = 7.30 Hz, CH _2, 2H), 3.91 (s, _CH3, 3H), 2.74 (s, CH ₃ , 3H), 1.46 (t, ³ J ( ¹ H, ¹ H) = 7.3 Hz, CH ₃ , 3H), 0.53 (qtq, 3H, BH ₃ , ¹ J ( ¹¹ B, ¹ H) = 84.4 Hz, ³ J ( ¹⁹ F, ¹ H) = 27.9 Hz, ⁴ J ( ¹⁹ F, ¹ H) = 3.85 Hz).
¹¹ B NMR (64.15 MHz, acetone-d6): δ = -33.3 (qt, ¹ J ( ¹¹ B, ¹ H) = 84.4 Hz, ² J ( ¹¹ B, ¹⁹ F) = 18.3 Hz) ppm.
¹¹ B { ¹ H} NMR (64.15 MHz, acetone-d6), δ, ppm: -33.3 (t, ² J ( ¹¹ B, ¹⁹ F) = 18.3 Hz).
¹⁹ F NMR (188.12 MHz, acetone-d6), δ, ppm: -84.5 (s, 3F, CF _3), -111.0 (qq, ² J ⁽¹⁹ F, ¹¹ B) = 18.3 Hz, ³ J ⁽¹⁹ F, ¹ H) = 27.8 Hz, 2F, CF ₂ ).
¹⁹ F { ¹ H} NMR (188.12 MHz, acetone-d6), δ, ppm: -84.4 (s, 3F, CF ₃ ), -111.0 (q, ² J ( ¹⁹ F, ¹¹ B) = 18.3 Hz, 2F, CF ₂ ).

Example 10: Synthesis of tetraethylammonium pentafluoroethyl trihydridoborate; [TEA] [C ₂ F ₅ BH ₃ ]

Sodium borohydride (Na [BH ₄ ], 7.6 g, 201 mmol) is suspended in THF (150 mL) and then treated with 44.2 mL of trimethylsilyl chloride (TMSCI) [(CH ₃ ) ₃ SiCl, 20.6 g, 190 mmol]. The reaction mixture is stirred for 15 hours at room temperature. In a second reaction vessel tetrahydrofuran (THF, 250 ml) is introduced, cooled to -78 ° C and degassed. Pentafluoroethane (C ₂ F ₅ H, 190 mmol, 22.8 g) is condensed in and n-BuLi (2.3 mol solution in hexane, 170 mmol, 74.0 mL) is slowly added dropwise over 60 min with vigorous stirring. The previously prepared BH ₃ · THF solution is cooled to -78 ° C and added to the reaction solution. The reaction mixture is then warmed slowly to room temperature and added to a solution of potassium carbonate (K ₂ CO ₃ , 13.8 g, 100 mmol) in 200 mL of deionized water. All volatile constituents (butane, hexane and THF) are removed and the aqueous phase is then treated with a solution of tetraethylammonium bromide ([TEA] Br, 42.0 g, 200 mmol) in 100 mL of deionized water. The resulting colorless solid is filtered off and dried in a fine vacuum (to 1 × 10 ^-3 mbar) (batch I). The aqueous filtrate is extracted with CH ₂ Cl ₂ (5 × 30 ml) and the organic solvent of the combined organic phases is distilled off. The solid obtained is then dried in a fine vacuum (to 1 × 10 ^-3 mbar) (batch II).
Yield of [Et ₄ N] [C ₂ F ₅ BH ₃ ]:
Batch I: 16.75 g, 63.6 mmol; Batch II: 6.99 g, 26.5 mmol;
Total: 23.74 g (90.1 mmol, 53% based on the amount of n-BuLi used).
Purity: 99% ( ¹¹ B NMR spectroscopy).

¹¹ B-NMR (160.46 MHz, acetone-d6), δ, ppm: -33.8 (qt, ¹ J ( ¹¹ B, ¹ H) = 91.2 Hz, ² J ( ¹¹ B, ¹⁹ F) = 20.0 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz, acetone-d6), δ, ppm: -33.8 (t, ² J ( ¹¹ B, ¹⁹ F) = 20.0 Hz).
¹⁹ F NMR (470.59 MHz, acetone-d6), δ, ppm: -84.7 (m, _CF3, 3F), 117.8 (tq, CF _2, 2F, ³ J ⁽¹⁹ F, ¹ H) = 22.72 Hz) ,
¹⁹ F ^{1 H} NMR (376.75 MHz, acetone-d6), δ, ppm: -84.7 (s, CF _3, 3F), 117.8 (q, CF _2, 2F, ² J ⁽¹⁹ F, ¹¹ B) = 20.3 Hz).
¹ H-NMR (500.13 MHz, acetone-d6), δ, ppm: 0.65 (qtq, ¹ J ( ¹ H, ¹¹ B) = 84.6 Hz, ³ J ( ¹ H, ¹⁹ F) = 27.3 Hz, ⁴ J ( ¹ H, ¹⁹ F) = 3.7 Hz), 1.2 (tt, ³ J ( ¹ H, ¹ H) = 7.3 Hz, ⁴ J ( ¹ H, ¹⁵ N) = 1.9 Hz), 3.1 (q, ³ J ( ¹ H, ¹ H) = 7.3 Hz).

Example 11: Preparation of a potassium pentafluoroethyl trihydridoborate solution, K [C ₂ F ₅ BH ₃ ] in THF

In the first step, a BH ₃ · THF solution is prepared. For this, Na [BH ₄ ] (2.50 g, 66.0 mmol) is initially charged and suspended in THF (100 ml). Subsequently, TMSCI (7.63 ml, 6.50 g, 60.0 mmol) is added dropwise and stirred at RT for 24 h. In the second step, THF (150 ml) is cooled to -78 ° C. in a further flask and then degassed. Thereafter, C ₂ F ₅ H (7.20 g, 60.0 mmol) is condensed in and cooled to 4 ° C n-BuLi (2.5 M in hexane, 22.0 ml, 55.0 mmol) slowly added dropwise with vigorous stirring over 30 min, with a slight yellow-brown color the reaction solution is observed. The prepared from step 1 BH ₃ · THF solution is cooled to -78 ° C and treated with the C ₂ F ₅ Li solution from step 2. Thereafter, the reaction mixture is slowly warmed to RT and added to a solution of K ₂ CO ₃ (4.20 g, 30.0 mmol) and H ₂ O (50.0 ml) and stirred at RT for 15 h. The two phases are separated and then the aqueous phase extracted with THF (3 × 30.0 ml). The combined organic phases are dried with K ₂ CO ₃ and filtered off.

The product is not isolated because K [C ₂ F ₅ BH ₃ ] is highly explosive and impact sensitive in the dry, crystalline state.

Yield: about 150 ml of a ca. 0.20 M solution corresponding to about 30 mmol K [C ₂ F ₅ BH ₃ ] (corresponding to 54% based on the n-BuLi used).

NMR data for K [C ₂ F ₅ BH ₃ ] in THF without deuterated solvent:
¹ H { ¹¹ B} NMR (199.93 MHz), δ, ppm: 0.41 (tq, ³ J ( ¹ H, ¹⁹ F) = 26.8 Hz, ⁴ J ( ¹ H, ¹⁹ F) = 3.5 Hz).
¹¹ B NMR (64.14 MHz), δ, ppm: -33.13 (dt, ¹ J ( ¹¹ B, ¹ H) = 84.2 Hz, ³ J ( ¹¹ B, ¹⁹ F) = 18.5 Hz).
¹¹ B ^{1 H} NMR (64.14 MHz), δ, ppm: -33.14 (t, ³ J ⁽¹¹ B, ¹⁹ F) = 18.5 Hz).
¹⁹ F { ¹ H} NMR (188.09 MHz), δ, ppm: -85.5 (s, 3F, CF ₃ ), -112.5 (q, ² J ( ¹⁹ F, ¹¹ B) = 18.6 Hz).
¹⁹ F-NMR (188.09 MHz), δ, ppm: -85.5 (q, ⁴ J ( ¹ H, ¹⁹ F) = ~ 3 Hz, 3F, CF ₃ ), -112.5 (dq, ³ J ( ¹⁹ F, ¹ H) = 26.1 Hz, ² J ( ¹⁹ F, ¹¹ B) = 18.5 Hz).

Example 12: Synthesis of tetramethylammonium trifluoromethyl trihydridoborate, [(CH ₃ ) ₄ N] [CF ₃ BH ₃ ].

A solution of BH ₃ · THF (-2.0 ± 0.1 M in THF, 0.43 mL, 0.860 mmol) is charged with TMSCF ₃ (0.10 mL, 0.677 mmol) in Et ₂ O (1 mL) and cooled to -90 ° C. Thereafter, tetramethylammonium fluoride ([TMA] F, 64 mg, 0.687 mmol) was added, the reaction solution was slowly warmed to RT in a cold bath and passed over Stirred overnight at RT. It forms a deep brown solution with a precipitate. Now a few milliliters of H ₂ O is added to the reaction mixture, whereupon the solid is dissolved and a two-phase system is formed. In the ¹¹ B NMR spectrum of the aqueous phase, the [CF ₃ BH ₃ ] ^- anion is detected by NMR spectroscopy.

NMR spectra of [(CH ₃ ) ₄ N] [CF ₃ BH ₃ ] in H ₂ O without deuterium lock:
¹¹ B-NMR (64.14 MHz, H ₂ O), δ, ppm: -33.2 (qq, ¹ J ( ¹¹ B, ¹ H) = 82.4 Hz, ² J ( ¹⁹ F, ¹¹ B) = 29.0 Hz,).
¹¹ B { ¹ H} NMR (64.14 MHz, H ₂ O), δ, ppm: -33.2 (q, ² J ( ¹⁹ F, ¹¹ B) = 29.1 Hz).
¹⁹ F-NMR (188.12 MHz, H ₂ O), δ, ppm: -49.0 (qq, ² J ( ¹⁹ F, ¹¹ B) = 28.9 Hz, ³ J ( ¹⁹ F, ¹ H) = 16.9 Hz).
¹⁹ F { ¹ H} NMR (188.12 MHz, H ₂ O), δ, ppm: -49.0 (q, ² J ( ¹⁹ F, ¹¹ B) = 28.9 Hz).

Example 13: Synthesis of tetrabutylammonium pentafluoroethyl dihydridocyanoborate, [TBA] [C ₂ F ₅ BH ₂ CN]

Part A) Synthesis of tetrabutylammonium pentafluoroethyldihydrido (trifluoromethylacetoxy) borate; [TBA] [C ₂ F ₅ BH ₂ (OC (O) CF ₃ )]

In a cylindrical reaction vessel with glass valve and PTFE spindle (Young, London, Rettberg, Göttingen), [TBA] [C ₂ F ₅ BH ₃ ] (3.0 g, 7.99 mmol) is weighed out and dissolved in 30 mL acetonitrile. Thereafter, the reaction solution is cooled to -10 ° C. with a cold bath (NaCl, ice). Trifluoroacetic acid, CF ₃ C (O) OH (1.82 g, 15.98 mmol, 1.22 mL) is then slowly added dropwise with vigorous stirring. The resulting gas (H ₂ ) is discharged through a bubble counter. The solution is stirred for 4 hours at room temperature. Subsequently, all volatile constituents are removed in a fine vacuum (1 × 10 ^-3 mbar). The highly viscous, oily residue is dissolved in acetonitrile (40 mL) and the solution is treated with potassium trifluoroacetate (1.2 g, 7.89 mmol). The valve of the flask is closed and the reaction mixture is heated at 60 ° C (oil bath temperature) for 30 hours. The volatile constituents are then condensed off and the residue is dried in a fine vacuum (1 × 10 ^-3 mbar). The solid is suspended in 20 mL deionized water and a solution of tetrabutylammonium bromide ([TBA] Br; 2.6 g, 8.07 mmol) in 30 mL deionized water is added. The precipitated solid is filtered off and dried in a fine vacuum (to 1 × 10 ^-3 mbar).
Yield of [TBA] [C ₂ F ₅ BH ₂ (OC (O) CF ₃ )]: 3.4 g (6.97 mmol, 87% based on the borate used).
Purity: 97% (confirmed ¹¹ B NMR spectroscopy)

¹¹ B-NMR (128.4 MHz, acetone-d6), δ, ppm: -9.85 (t, ¹ J ( ¹¹ B, ¹ H) = 102 Hz).
¹¹ B { ¹ H} NMR (128.4 MHz, Acton-d6), δ, ppm: -9.85 (s).
¹⁹ F-NMR (376.7 MHz, acetone-d6), δ, ppm: -76.4 (s, CF _3, 3F, Trifluormethylacetoxy group), -84.2 (s, CF _3, 3F, pentafluoroethyl group), -127.2 ( q), CF ₂ , 2F.
¹ H-NMR (400.4 MHz, acetone-d6), δ, ppm: 0.7 (t, _CH3, 3H, ³ J ⁽¹ H, ¹ H) = 7.4 Hz, cation), 1.18 (sx, CH _2, 2H ,, ³ J ( ¹ H, ¹ H) = 7.5 Hz, cation), 1.57 (m, CH ₂ , 2H, cation), 3.19 (m, CH ₂ , 2H, cation).

Part B) Synthesis of tetrabutylammonium pentafluoroethyl dihydridocyanoborate; [TBA] [C ₂ F ₅ BH ₂ CN]

In a cylindrical reaction vessel with glass valve and PTFE spindle (Young, London, Rettberg, Göttingen), 700 mg (1.43 mmol) of tetrabutylammonium pentafluoroethyldihydrido (trifluoromethylacetoxy) borate, [TBA] [C ₂ F ₅ BH ₂ (OC (O) CF ₃ ] ], and treated with (CH ₃ ) ₃ SiCN (12.0 mL). Subsequently, the reaction mixture is stirred for 150 minutes in a microwave at a constant power of 220 W. The solvent is then condensed off and all volatile constituents are removed in a fine vacuum (1 × 10 ^-3 mbar). The residue is dissolved in acetone (2 ml) and the solid substance is precipitated with the addition of pentane (30 ml). The supernatant solution is decanted off and the solid is dried in a fine vacuum (1 × 10 ^-3 mbar).
Yield: 390 mg (0.97 mmol, 68% with respect to the amount of [TBA] [C ₂ F ₅ BH ₂ (OC (O) CF ₃ ]) used.
Purity: 92% (confirmed by ¹¹ B NMR spectroscopy).

¹¹ B NMR (160.46 MHz, acetone-d6), δ, ppm: -33.8 (tt, ¹ J ( ¹¹ B, ¹ H) = 91.2 Hz, ² J ( ¹¹ B, ¹⁹ F) = 20.0 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz, acetone-d6), δ, ppm: -33.8 (t, ² J ( ¹¹ B, ¹⁹ F) = 20.0 Hz).
¹⁹ F NMR (470.59 MHz, acetone-d6), δ, ppm: -84.7 (m, _CF3, 3F), 117.8 (tq, CF _2, 2F, ³ J ⁽¹⁹ F, ¹ H) = 22.72 Hz) ,
¹⁹ F ^{1 H} NMR (376.75 MHz, acetone-d6), δ, ppm: -84.7 (s, CF _3, 3F), 117.8 (q, CF _2, 2F, ² J ⁽¹⁹ F, ¹¹ B) = 20.3 Hz).
¹ H-NMR (500.13 MHz, acetone-d6), δ, ppm: 0.92 (t, ¹ J ( ¹ H, ¹ H) = 7.4 Hz), 1.38 (sx, ³ J ( ¹ H, ¹ H) = 7.5 Hz), 1.87 (qi, ¹ J ( ¹ H, ¹ H) = 7.9 Hz), 3.46 (m)).

Example 14: Synthesis of tetraethylammonium pentafluoroethyldihydrido (trifluoromethylacetoxy) borate; [TEA] [C ₂ F ₅ BH ₂ (OC (O) CF ₃ )]

In a cylindrical reaction vessel with glass valve and PTFE spindle (Rettberg, Göttingen), tetraethylammonium pentafluoroethyl trihydridoborate ([Et ₄ N] [C ₂ F ₅ BH ₃ ], 8.0 g, 30.4 mmol) is weighed out and dissolved in acetonitrile (120 mL). Thereafter, the reaction solution is cooled to 0 ° C with a cold bath. Trifluoroacetic acid (CF ₃ C (O) OH, 10.4 g, 91.2 mmol, 6.98 mL) is then added slowly with vigorous stirring. The resulting gas (H ₂ ) is discharged through a bubble counter. The solution is stirred for one hour at 0 ° C. Subsequently, all volatile constituents are removed in a fine vacuum (up to 1 × 10 ^-3 mbar). The resulting highly viscous oily residue is dissolved in THF (80 mL) and the solution is treated with CF ₃ C (O) OK (1.5 g, 9.86 mmol). The valve of the flask is closed and the reaction mixture is stirred for one hour at 75 ° C (oil bath temperature). The volatiles are removed in vacuo, the residue dried in a fine vacuum (to 1 x 10 ^-3 mbar) and then suspended in deionized water (10 mL). A solution of tetraethylammonium bromide (Et ₄ NBr solution, 6.3 g, 30.0 mmol in deionized water (20 mL)) is added. The aqueous solution is then extracted with CH ₂ Cl ₂ (5 × 10 mL), the organic phases combined, the CH ₂ Cl ₂ removed in vacuo and the remaining [Et ₄ N] [C ₂ F ₅ BH ₂ (OC (O ) CF ₃ )] in a fine vacuum (to 1 x 10 ^-3 mbar) dried.
Yield of [Et ₄ N] [C ₂ F ₅ BH ₂ (OC (O) CF ₃ )]: 9.75 g (26.0 mmol, 86% based on the [Et ₄ N] [C ₂ F ₅ BH ₃ ] used) ,
Purity: 89% ( ¹¹ B NMR spectroscopy).

¹¹ B NMR (160.46 MHz, acetone-d6), δ, ppm: -9.85 (t, ¹ J ( ¹¹ B, ¹ H) = 102 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz, Acton-d6), δ, ppm: -9.85 (s).
¹⁹ F NMR (470.59 MHz, acetone-d6), δ, ppm: -76.4 (s, CF _3, 3F, CF ₃ C (O) O-group), -84.2 (s, CF _3, 3F, C ₂ F ₅ group), -127.2 (q, CF ₂ , 2F).
¹ H-NMR (500.13 MHz, acetone-d6), δ, ppm: 1.2 (tt, ³ J ( ¹ H, ¹ H) = 7.3 Hz, ⁴ J ( ¹ H, ¹⁵ N) = 1.9 Hz), 3.1 ( q, ³ J ( ¹ H, ¹ H) = 7.3 Hz).

Example 15. Synthesis of tetrabutylammonium pentafluoroethylhydridodipropoxyborate; [TBA] [C ₂ F ₅ BH (O ₂ C ₃ H ₅ ) ₂ ]

[n -Bu ₄ N] [C ₂ F ₅ BH ₃ ] (3.75 g, 10 mmol) is dissolved in dichloromethane (100 mL). Thereafter, propionic acid (40.34 g, 544.7 mmol, 40.8 mL) is added, with gas evolution (H ₂ ) occurring. The reaction solution is stirred for 24 h at room temperature. Subsequently, all volatile constituents are removed in a fine vacuum (1 × 10 ^-3 mbar) and the liquid residue is taken up in deionized H ₂ O (20 ml). The solution is extracted with Et ₂ O (5 × 10 mL) and the combined organic phases are concentrated to dryness using a rotary evaporator. The solid obtained is dried in a fine vacuum (1 × 10 ^-3 mbar).
Yield: 4.6 g (8.8 mmol, 88% with respect to [n-Bu ₄ N] [C ₂ F ₅ BH ₃ ]).
Purity: 97% ⁽¹⁹ F-NMR spectroscopy).

¹¹ B NMR (160.46 MHz, CD ₂ Cl ₂ ), δ, ppm: -3.98 (d, ¹ J ( ¹¹ B, ¹ H) = 95.1 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz, CD ₂ Cl ₂ ), δ, ppm: -3.98 (s).
¹⁹ F NMR (470.59 MHz, CD ₂ Cl ₂₎ δ, ppm: -83.8 (m, _CF3, 3F), -133.7 (m, CF _2, 2F).
¹ H-NMR (500.13 MHz, CD ₂ Cl ₂ ), δ, ppm: 1.04 (t, ³ J ( ¹ H, ¹ H) = 7.49 Hz), 1.06 (t, ³ J ( ¹ H, ¹ H) 7.5 Hz), 1.43 (tq, ³ J ( ¹ H, ¹ H) = 7.5 Hz), 1.67 (m), 2.26 (q, ³ J ( ¹ H, ¹ H) = 7.5 Hz), (q, 3.2 ( m).
¹ H { ¹¹ B} NMR (500.13 MHz, CD ₂ Cl ₂ ), δ, ppm: 1.04 (t, ³ J ( ¹ H, ¹ H) = 7.49 Hz), 1.06 (t, ³ J ( ¹ H, ¹ H) = 7.5 Hz), 1.43 (tq, ³ J ( ¹ H, ¹ H) = 7.5 Hz), 1.67 (m), 2.26 (q, ³ J ( ¹ H, ¹ H) = 7.5 Hz), 3.2 (m), 3.44 (t, ³ J ( ¹ H, ¹⁹ F) = 11.5 Hz).

Example 16. Synthesis of tetrabutylammonium pentafluoroethyldicyanohydridoborate; [TBA] [C ₂ F ₅ BH (CN) ₂ ]

[n-Bu ₄ N] [C ₂ F ₅ BH (O ₂ C ₃ H ₅ ) ₂ ] (33 mg, 0.07 mmol) is placed in an NMR tube with glass valve and Teflon spindle and in (CH ₃ ) ₃ SiCN ( 0.5 mL, 4.00 mmol). Subsequently, (CH ₃ ) ₃ SiCl (0.1 mL, 0.786 mmol) is added and the reaction solution is heated at 130 ° C. for 30 h (bath temperature). Thereafter, all volatile constituents are removed in a fine vacuum (1 × 10 ^-3 mbar) and the residue is dissolved in CDCl ₃ . The formation of by Tetrabutylammoniumpentafluorethyldicyanohydridoborat, [n-Bu ₄ N] [C ₂ F ₅ BH (CN) _2]) is detected by NMR spectroscopy.
Purity: 95% ( ¹¹ B NMR spectroscopy).

¹ B NMR (160.46 MHz, CDCl ₃ ), δ, ppm: -32.9 (dt, ¹ J ( ¹¹ B, ¹ H) = 96.5 Hz, ² J ( ¹¹ B, ¹⁹ F) = 19.1 Hz).
¹¹ B ^{1 H} NMR (160.46 MHz, CDCl ₃₎ δ, ppm: -32.9 (t, ² J ⁽¹¹ B, ¹⁹ F) = 19.1 Hz).
¹⁹ F NMR (470.59 MHz, CDCl ₃₎ δ, ppm: -83.5 (m, _CF3, 3F), -121.2 (m, CF _2, 2F).
¹⁹ F ^{11 B} NMR (470.59 MHz, CDCl ₃₎ δ, ppm: -83.5 (m, _CF3, 3F), -121.2 (dq, ³ J ⁽¹⁹ F, ¹ H) = 19.2 Hz, ³ J ( ¹⁹ F, ¹⁹ F) = 1.06 Hz).
¹ H-NMR (500.13 MHz, CDCl ₃₎ δ, ppm: 1:04 (t, ³ J ⁽¹ H, ¹ H) = 7.3 Hz), 1:45 (tq, ³ J ⁽¹ H, ¹ H) = 7.5 Hz ), 1.63 (m), 3.2 (m).
¹ H ^{11 B} NMR (500.13 MHz, CDCl ₃₎ δ, ppm: 1:04 (t, ³ J ⁽¹ H, ¹ H) = 7.3 Hz), 1:45 (tq, ³ J ⁽¹ H, ¹ H ) = 7.5 Hz), 1.63 (m), 1.86 (tq, ³ J ( ¹ H, ¹⁹ F) = 19.2 Hz, ⁴ J ( ¹ H, ¹⁹ F) = 2.04 Hz), 3.2 (m).

Example 17. Synthesis of tetrabutylammonium pentafluoroethylhydrido-isocyanopropoxyborate, [TBA] [C ₂ F ₅ BH (NC) (O ₂ C ₃ H ₅ )]

[n-Bu ₄ N] [C ₂ F ₅ BH (O ₂ C ₃ H ₅ ) ₂ ] (519 mg, 1.0 mmol) is initially charged and dissolved in (CH ₃ ) ₃ SiCN (5 mL, 3.965 g, 39.9 mmol). solved. Thereafter, (CH ₃ ) ₃ SiCl (1.25 mL, 1.07 g, 9.83 mmol) is added and the reaction solution is stirred for 24 h at room temperature. All volatile constituents are removed in a fine vacuum (1 × 10 ^-3 mbar) and the oily residue is dissolved in CDCl ₃ and analyzed by NMR spectroscopy.
Purity: 97% ( ¹¹ B NMR spectroscopy).
¹¹ B-NMR (160.46 MHz, CDCl ₃₎ δ, ppm: -10.3 (m).
¹¹ B ^{1 H} NMR (160.46 MHz, CDCl ₃₎ δ, ppm: -10.3 (s).
¹⁹ F NMR (470.59 MHz, CDCl ₃₎ δ, ppm: -82.7 (m, _CF3, 3F), -131.6 (d, ² J ⁽¹⁹ F, ¹⁹ F) = 315.7 Hz), -133.5 (d , ² J ( ¹⁹ F, ¹⁹ F) = 315.7 Hz).
¹⁹ F ^{11 B} NMR (470.59 MHz, CDCl ₃₎ δ, ppm: -82.7 (m, _CF3, 3F), -131.6 (dd, ² J ⁽¹⁹ F, ¹⁹ F) = 315.7 Hz, ³ J ( ¹⁹ F, ¹ H) = 11.8 Hz), -133.5 (dd, ² J ( ¹⁹ F, ¹⁹ F) = 315.7 Hz, ³ J ( ¹⁹ F, ¹ H) = 11.8 Hz).
¹ H-NMR (500.13 MHz, CDCl ₃ ), δ, ppm: 0.98 (t, ³ J ( ¹ H, ¹ H) = 7.56 Hz), 1.03 (t, ³ J ( ¹ H, ¹ H) = 7.5 Hz ), 1.41 (tq, ³ J ( ¹ H, ¹ H) = 7.3 Hz), 1.62 (m), 2.26 (q, ³ J ( ¹ H, ¹ H) = 7.5 Hz), 3.2 (m).
¹ H { ¹¹ B} NMR (500.13 MHz, CDCl ₃ ), δ, ppm: 0.98 (t, ³ J ( ¹ H, ¹ H) = 7.56 Hz), 1.03 (t, ³ J ( ¹ H, ¹ H ) = 7.5 Hz), 1.41 (tq, ³ J ( ¹ H, ¹ H) = 7.3 Hz), 1.62 (m), 2.26 (q, ³ J ( ¹ H, ¹ H) = 7.5 Hz), 2.94 (t , ³ J ( ¹ H, ¹⁹ F) = 12.9 Hz), 3.2 (m).

Example 18. Synthesis of tetrabutylammonium pentafluoroethyl cyanohydrido-propoxyborate, [TBA] [C ₂ F ₅ BH (CN) (O ₂ C ₃ H ₅ )]

In a NMR tube with glass valve and Teflon spindle, [n-Bu ₄ N] [C ₂ F ₅ BH (O ₂ C ₃ H ₅ ) ₂ ] (33 mg, 0.07 mmol) is initially charged and in (CH ₃ ) ₃ SiCN ( 0.5 mL, 4.00 mmol). Then (CH ₃ ) ₃ SiCl (0.1 ml, 0.786 mmol) is added and the reaction solution is heated for 3.5 h at 100 ° C (bath temperature), all volatile constituents are removed in a fine vacuum (1 x 10 ^-3 mbar). The residue obtained is dissolved in CDCl ₃ and the solution is analyzed by NMR spectroscopy.
Purity: 99% ( ¹¹ B NMR spectroscopy).
¹ B NMR (160.46 MHz, CDCl ₃ ), δ, ppm: -15.03 (d, ¹ J ( ¹¹ B, ¹ H) = 104.8 Hz).
¹¹ B ^{1 H} NMR (160.46 MHz, CDCl ₃₎ δ, ppm: -15.03 (s).
¹⁹ F NMR (470.59 MHz, CDCl ₃₎ δ, ppm: -82.9 (m, _CF3, 3F), -127.5 (d, ² J ⁽¹⁹ F, ¹⁹ F) = 315 Hz), -129.2 (d , ² J ( ¹⁹ F, ¹⁹ F) = 315 Hz).

Example 19: Synthesis of N-butyl-N-methylpyrrolidinium pentafluoroethyl dihydridocyanoborate; [BMPL] [C ₂ F ₅ BH ₂ (CN)]

In a cylindrical reaction vessel with glass valve and PTFE spindle (Rettberg, Göttingen), tetraethylammonium pentafluoroethyltrihydridoborate ([Et ₄ N] [C ₂ F ₅ BH ₃ ], 2.0 g, 7.6 mmol) is weighed out and dissolved in acetonitrile (20 mL). Thereafter, the reaction solution is cooled to 0 ° C. with an ice bath, and trifluoroacetic acid (CF ₃ C (O) OH, 2.6 g, 22.8 mmol, 1.75 mL) is slowly added with vigorous stirring. The resulting gas (H ₂ ) is discharged through a bubble counter. The solution is stirred for one hour at 0 ° C. and then for 30 minutes at room temperature. Subsequently, all volatile constituents are removed in a fine vacuum (up to 1 × 10 ^-3 mbar). The resulting highly viscous residue is dissolved in THF (10 ml) and potassium trifluoroacetate (CF ₃ C (O) OK, 1.14 g, 7.5 mmol) is added. The valve of the flask is closed and the reaction mixture stirred for one hour at 75 ° C (oil bath temperature). The volatiles are condensed off and a solution of tetraethylammonium bromide ([TEA] Br solution, 1.68 g, 8.0 mmol in 10 mL deionized water) is added. Thereafter, the reaction mixture is extracted with CH ₂ Cl ₂ (4 × 5 mL) and the combined organic phases are concentrated in vacuo to dryness. The resulting residue is dried in a fine vacuum (to 1 x 10 ^-3 mbar) and then dissolved in trimethylsilyl cyanide (TMSCN, (CH ₃ ) ₃ SiCN, 11.8 g, 112.5 mmol, 15.0 mL). The reaction mixture is then irradiated in a closed reaction vessel for 150 min in a microwave (CEM Discover) (220 W). All volatiles are then condensed off and the residue is dissolved in 10% HCl (20 mL). The aqueous solution is extracted with Et ₂ O (5 x 10 mL). Thereafter, the combined organic phases are treated with a solution of K ₂ CO ₃ (1.03 g, 7.5 mmol) in deionized H ₂ O (20 mL) and the ether is distilled off. The remaining aqueous solution is then extracted with THF (5 × 10 mL). The combined THF phases are concentrated to dryness. The resulting residue is taken up in deionized H ₂ O (20 mL) and treated with a solution of N-butyl-N-methylpyrrolidinium chloride ([BMPL] Cl, 1.40 g, 8.0 mmol) in deionized H ₂ O (10 mL). The aqueous solution is then extracted with CH ₂ Cl ₂ (5 × 10 mL), the organic phases combined and the CH ₂ Cl ₂ removed. The liquid obtained is dried in a fine vacuum (to 1 × 10 ^-3 mbar).
Yield of [BMPL] [C ₂ F ₅ BH ₂ (CN)]: 710 mg (2.38 mmol, 32% based on the amount of [Et ₄ N] [C ₂ F ₅ BH ₃ ] used).

¹¹ B NMR (160.46 MHz, acetone-d6), δ, ppm: -33.8 (tt, ¹ J ( ¹¹ B, ¹ H) = 91.2 Hz, ² J ( ¹¹ B, ¹⁹ F) = 20.0 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz, acetone-d6), δ, ppm: -33.8 (t, ² J ( ¹¹ B, ¹⁹ F) = 20.0 Hz).
¹⁹ F NMR (470.59 MHz, acetone-d6), δ, ppm: -84.7 (m, _CF3, 3F), 117.8 (tq, CF _2, 2F, ³ J ⁽¹⁹ F, ¹ H) = 22.72 Hz) ,
¹⁹ F ^{1 H} NMR (376.75 MHz, acetone-d6), δ, ppm: -84.7 (s, CF _3, 3F), 117.8 (q, CF _2, 2F, ² J ⁽¹⁹ F, ¹¹ B) = 20.3 Hz).
¹ H-NMR (500.13 MHz, acetone-d6), δ, ppm: 0.99 (t, ³ J ( ¹ H, ¹ H) = 7.35 Hz, 3H, CH ₃ ), 1.37 (sx, ³ J ( ¹ H, ¹ H) = 7.41 Hz, 2H, CH ₂ ), 1.85 (qi, ³ J ( ¹ H, ¹ H) = 8.10 Hz, 2H, CH ₂ ), 2.26 (m), 3.20 (s, CH ₃ , 3H) , 3.49 (m, 2H, CH ₂ ), 3.67 (m).

Example 20: Synthesis of 1-ethyl-3-methylimidazolium pentafluoroethylcyanodihydridoborate, [EMIM] [C ₂ F ₅ BH ₂ (CN)]

In a cylindrical reaction vessel with glass valve and PTFE spindle (Rettberg, Göttingen) Tetraethylammoniumpentafluorethyltrihydridoborat ([Et₄N] [C₂F₅bra₃]; 1.0 g, 3.8 mmol) and dissolved in acetonitrile (15 mL). Thereafter, the reaction solution is cooled with an ice bath to 0 ° C and with vigorous stirring trifluoroacetic acid (CF₃C (O) OH; 1.3 g, 11.4 mmol, 0.87 mL) was added slowly. The resulting gas (H₂) is derived by a bubble counter. The solution is stirred at 0 ° C. for 30 minutes and then at room temperature for 30 minutes. Subsequently, in a fine vacuum (to 1 · 10^-3 mbar) all volatiles removed. The resulting high-viscosity residue is dissolved in THF (10 ml) and treated with potassium trifluoroacetate (CF₃COOK; 578 mg, 3.8 mmol). The valve of the flask is closed and the reaction mixture stirred for one hour at 75 ° C (oil bath temperature). The volatiles are condensed off and a solution of tetraethylammonium bromide ([TEA] Br solution, 840 mg, 4 mmol in 10 mL deionized water) is added. Thereafter, the reaction mixture with CH₂Cl₂ extracted (4 × 5 mL) and the combined organic phases are concentrated in vacuo to dryness. The residue obtained is dried in a fine vacuum (until 1 × 10^-3 mbar) and then in trimethylsilyl cyanide (TMSCN, (CH₃)₃SiCN; 11.8 g, 0.12 mol, 15.0 mL). The reaction mixture is then irradiated in a closed reaction vessel for 150 min in a microwave (CEM Discover) (220 W). All volatiles are then condensed off and the residue is dissolved in 10% HCl (20 mL). The aqueous solution is washed with Et₂Extracted O (4 x 20 mL). Thereafter, the combined organic phases are treated with a solution of K₂CO₃ (1.0 g, 7.23 mmol) in 20 mL of deionized H₂O is added and the ether is distilled off. The remaining aqueous solution is then extracted with THF (4 × 20 mL). The combined THF phases are concentrated to dryness. The residue obtained is in deionized H₂O (100 mL) is added and 1-ethyl-3-methylimidazolium chloride ([EMIM] Cl; 600 mg, 4.0 mmol) is added. Subsequently, the aqueous solution with CH₂Cl₂ (4 x 20 mL), the organic phases combined and the CH₂Cl₂ away. The resulting liquid is in a fine vacuum (to 1 x 10^-3 mbar).
Yield of [EMIM] [C₂F₅bra₂(CN)]: 547 mg (2.03 mmol, 54% based on the amount of [Et₄N] [C₂F₅bra₃]).
Purity: 98% (¹¹B-NMR spectroscopy confirmed).

¹¹B NMR (160.46 MHz, acetone-d6), δ, ppm: -33.8 (tt,¹J (¹¹B¹H) = 91.2 Hz,²J (¹¹B¹⁹F) = 20.0 Hz).
¹¹B {¹H} -NMR (160.46 MHz, acetone-d6), δ, ppm: -33.8 (t,²J (¹¹B¹⁹F) = 20.0 Hz).
¹⁹F NMR (470.59 MHz, acetone-d6), δ, ppm: -84.7 (m, CF₃, 3F), 117.8 (tq, CF₂, 2F,³J (¹⁹F,¹H) = 22.72 Hz).
¹⁹F {¹H} NMR (376.75 MHz, acetone-d6), δ, ppm: -84.7 (s, CF₃, 3F), 117.8 (q, CF₂, 2F,²J (¹⁹F,¹¹B) = 20.3 Hz).
¹H-NMR (500.13 MHz, acetone-d6), δ, ppm: 1.08 (tq,¹J (¹H,¹¹B) = 91.18 Hz,³J (¹H,¹⁹F) = 23.1 Hz), 1.56 (t, CH₃, 3H,³J (¹H,¹H) = 7.23 Hz), 4.04 (s, CH₃, 3H), 4.39 (q, CH₂, 2H,³J (¹H,¹H) = 7.30 Hz), 7.68 (t, 1H), 7.71 (t, 1H), 9.1 (s, 1H).
¹H{¹¹B} NMR (500.13 MHz, acetone-d6), δ, ppm: 1.08 (tq,³J (¹H,¹⁹F) = 23.7 Hz,⁴J (¹H,¹⁹F) = 2.82 Hz), 1.56 (t, CH₃, 3H,³J (¹H,¹H) = 7.23 Hz), 4.04 (s, CH₃, 3H), 4.39 (q, CH₂, 2H,³J (¹H,¹H) = 7.30 Hz), 7.68 (t, 1H), 7.71 (t, 1H), 9.1 (s, 1H).

Example 21. Synthesis of pentafluoroethyldihydridoborane THF adduct, C ₂ F ₅ BH ₂ .THF

A)

Tetrabutylammonium pentafluoroethyl trihydridoborate, [TBA] [C ₂ F ₅ BH ₃ ], (2.00 g, 5.30 mmol) is initially charged and dissolved in THF (150 mL). Subsequently, iodine (676 mg, 2.10 mmol) is weighed in separately and dissolved in THF (20.0 ml). Thereafter, both solutions are cooled to 0 ° C and slowly added dropwise the iodine solution to the THF solution of [TBA] [C ₂ F ₅ BH ₃ ] with vigorous stirring. This gives a yellowish color, which disappears relatively quickly. After the addition of the iodine solution, the reaction mixture is filtered inert and the filtrate is concentrated to 10.0 ml.
Yield: about 10 ml of a ca. 0.5 M solution in THF (5.00 mmol).

B)

K [C ₂ F ₅ BH ₃ ] in THF (15.0 ml, 0.14 M, 2.10 mmol) is initially charged. Thereafter, with stirring, trimethylsilyl chloride, TMSCl (0.27 ml, 228 mg, 2.10 mmol) is added dropwise, with an immediate turbidity of the solution and slight evolution of gas is observed. Subsequently, the solution is stirred for five hours at RT.
Yield: approx. 15.0 ml of a 0.14 M solution in THF.

NMR data of the solution of C ₂ F ₅ BH ₂ .THF in undeuterated THF:

¹ H-NMR (500.13 MHz), δ, ppm: 1.72 (BH ₂ , unresolved) ppm.
¹ H { ¹¹ B} NMR (500.13 MHz), δ, ppm: 1.72 (t, BH ₂ , ³ J ( ¹¹ B, ¹⁹ F) = 18.2 Hz).
¹¹ B NMR (160.46 MHz), δ, ppm: -2.86 (t, ¹ J ( ¹¹ B, ¹ H) = 108.2 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz), δ, ppm: -2.86 (s, BH ₂ ).
¹⁹ F-NMR (470.59 MHz), δ, ppm: -85.8 (m, CF ₃ ), -128.0 (m, CF ₂ ).
¹³ C { ¹ H} NMR (125.75 MHz), δ, ppm: 24.6 (s, CH ₂ , THF), 66.4 (s, CH ₂ , THF), 120.7 (qt, CF ₃ , ¹ J ( ¹³ C, ¹⁹ F) = 284.8, ² J ( ¹³ C, ¹⁹ F) = 32.6 Hz).
¹³ C { ¹⁹ F} NMR (125.75 MHz), δ, ppm: 24.6 (t, CH ₂ , THF, ¹ J ( ¹³ C, ¹ H) = 132.1 Hz), 66.4 (t, CH ₂ , THF, ¹ J ( ¹³ C, ¹ H) = 143.9 Hz), 120.7 (s, CF ₃ )
¹³ C { ¹¹ B, ¹ H} NMR (75.48 MHz), δ, ppm: 24.6 (s, CH ₂ , THF), 66.4 (s, CH ₂ , THF), 120.7 (qt, CF ₃ , ¹ J ( ¹³ C, ¹⁹ F) = 284.8, ² J ( ¹³ C, ¹⁹ F) = 32.6 Hz), 122.3 (tq, CF ₂ , ¹ J ( ¹³ C, ¹⁹ F) = 256.4 Hz, ² J ( ¹³ C, ¹⁹ F) = 36.5 Hz).

Example 22. Synthesis of pentafluoroethyldihydridoborane-pyridine adduct, C ₂ F ₅ BH ₂ .Py

A)

Tetrabutylammonium pentafluoroethyl trihydridoborate, [n -Bu ₄ N] [C ₂ F ₅ BH ₃ ], (2.38 g, 6.3 mmol) is dissolved in pyridine (20 mL, 0.25 mol). Thereafter, the solution is cooled with an ice bath (0 ° C bath temperature) and slowly added in portions with iodine (1.6 g, 6.3 mmol). Gas development starts here. After completion of gas evolution, the pyridine is removed in a fine vacuum (1 × 10 ^-3 mbar) and the resulting dark orange solid is suspended in Et ₂ O (100 mL). The reaction mixture is then filtered inert and the filtrate is concentrated in a fine vacuum. Then pentane (55 mL) is added, forming an orange-yellow oil. This is separated from the pentane solution, admixed with Et ₂ O (5 mL) and the solution washed with an aqueous, saturated sodium thiosulfate solution (3 x 2 mL). The solvent of the organic phase (Et ₂ O) is removed in a fine vacuum (1 x 10 ^-3 mbar) and the resulting oily, pale yellow residue in a fine vacuum (1 x 10 ^-3 mbar) dried.

Yield: 209 mg (0.99 mmol, 16% based on [n-Bu ₄ N] [C ₂ F ₅ BH ₃ ]).
Purity: 99% ( ¹¹ B NMR spectroscopy).

NMR data of C ₂ F ₅ BH ₂ · Py:
¹¹ B-NMR (160.46 MHz, CDCl ₃ ), δ, ppm: -9.46 (t, ¹ J ( ¹¹ B, ¹ H) = 101.2 Hz).
¹¹ B ^{1 H} NMR (160.46 MHz, CDCl ₃₎ δ, ppm: -9.46 (s).
¹⁹ F NMR (470.59 MHz, CDCl ₃₎ δ, ppm: -83.8 (m, _CF3, 3F), -125.8 (m, CF _2, 2F).
¹ H-NMR (500.13 MHz, CDCl ₃₎ δ, ppm: 2.73 (m, ¹ J ⁽¹ H, ¹¹ B) = 87.5 Hz), 7.70 (m, CH, Py), 8.16 (m, CH, Py ), 8.62 (m, CH, Py).
¹ H { ¹¹ B} NMR (500.13 MHz, CDCl ₃ ), δ, ppm: 2.73 (tq, ³ J ( ¹ H, ¹⁹ F) = 20.05 Hz, ⁴ J ( ¹ H, ¹⁹ F) = 2.26 Hz) 7.70 (m, CH, Py), 8.16 (m, CH, Py), 8.62 (m, CH, Py).

B)

Tetrabutylammonium pentafluoroethyl trihydridoborate, [TBA] [C ₂ F ₅ BH ₃ ], (1.00 g, 2.66 mmol) is dissolved in pyridine (10.0 mL). Thereafter, iodine (667 mg, 2.62 mmol) is dissolved in pyridine (10.0 ml) separately. Subsequently, the iodine solution is slowly added dropwise to the reaction solution at 0 ° C, with a yellowish to brown coloration is observed, but disappears after some time. After complete addition of the iodine solution, the pyridine is removed in a fine vacuum (1 × 10 ^-3 mbar). A light yellow solid remains, which is suspended in diethyl ether (40.0 ml). The suspension is then filtered inert and the solid washed with Et ₂ O. The Et ₂ O solution is condensed off and the orange, liquid residue is dried in a fine vacuum (1 × 10 ^-3 mbar).
Yield: 270 mg of an orange liquid (1.30 mmol, corresponding to 49% with respect to the borate used).
Purity: 98% ( ¹⁹ F NMR spectroscopy).

NMR data of C ₂ F ₅ BH ₂ · Py:
¹ H-NMR (500.13 MHz), δ, ppm: 2.72 (q, BH ₂ , ¹ J ( ¹ H, ¹¹ B) = 99.1 Hz), 7.96 (m, 2H, pyridine), 8.44 (tt, 1H, pyridine , ³ J ( ¹ H, ¹ H) = 7.7 Hz, ⁴ J ( ¹ H, ¹ H) = 1.5 Hz), 8.7 (m, 2H, pyridine).
¹ H { ¹¹ B} NMR (500.13 MHz), δ ppm: 2.72 (tq, BH ₂ , ³ J ( ¹ H, ¹⁹ F) = 20.3 Hz, ⁴ J ( ¹ H, ¹⁹ F) = 2.6 Hz)) , 7.96 (m, 2H, pyridine), 8.44 (tt, 1H, pyridine, ³ J ( ¹ H, ¹ H) = 7.7 Hz, ⁴ J ( ¹ H, ¹ H) = 1.5 Hz), 8.7 (m, 2H , Pyridine).
¹¹ B NMR (160.46 MHz), δ, ppm: -9.72 (t, BH ₂ , ¹ J ( ¹¹ B, ¹ H) = 101.7 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz), δ, ppm: -9.72 (s, BH ₂ ).
¹¹ B { ¹⁹ F} NMR (160.46 MHz), δ, ppm: -10.62 (t, BH ₂ , ¹ J ( ¹¹ B, ¹⁹ F) = 102.0 Hz).
¹⁹ F NMR (470.59 MHz), δ, ppm: -84.4 (dd, CF _3, ³ J ⁽¹⁹ F, ¹⁹ F) = 2.6 Hz, ⁴ J ⁽¹⁹ F, ¹ H) = 1.2 Hz), -126.1 (m, CF ₂ ).
¹⁹ F { ¹¹ B} NMR (470.59 MHz), δ, ppm: -84.4 (tt, CF ₃ , ³ J ( ¹⁹ F, ¹⁹ F) = 2.6 Hz, ⁴ J ( ¹⁹ F, ¹ H) = 1.2 Hz ), -126.1 (t, CF ₂ , ³ J ( ¹⁹ F, ¹ H) = 20.2 Hz).
¹³ C { ¹ H} NMR (125.75 MHz), δ, ppm: 121.8 (qt, CF ₃ , 1C, ¹ J ( ¹³ C, ¹⁹ F) = 284.4 Hz, ² J ( ¹³ C, ¹⁹ F) = 32.7 Hz), 126.4 (s, CH, pyridine), 142.4 (s, CH, pyridine), 148.7 (s, CH, pyridine).
¹³ C { ¹¹ B, ¹ H} NMR (75.48 MHz), δ, ppm: 121.8 (qt, CF ₃ , 1C, ¹ J ( ¹³ C, ¹⁹ F) = 284.4 Hz, ² J ( ¹³ C, ¹⁹ F ) = 32.7 Hz), 124.5 (tq, CF ₂ , 1C, ¹ J ( ¹³ C, ¹⁹ F) = 257.3 Hz, ² J ( ¹³ C, ¹⁹ F) = 36.4 Hz), 126.4 (s, CH, pyridine) , 142.4 (s, CH, pyridine), 148.7 (s, CH, pyridine).

Example 23. Synthesis of pentafluoroethyldihydridoborane acetonitrile adduct, C ₂ F ₅ BH ₂ .NCCH ₃

Tetrabutylammonium pentafluoroethyl trihydridoborate, [n -Bu ₄ N] [C ₂ F ₅ BH ₃ ] (10.0 g, 26.7 mmol) is dissolved in acetonitrile (100 mL, 1.92 mmol). Thereafter, the solution is cooled with an ice bath (0 ° C bath temperature) and slowly added iodine (3.35 g, 13.2 mmol) in portions. Gas development starts here. All volatiles are then removed in a fine vacuum (1 x 10 ^-3 mbar) and the residue is suspended in Et ₂ O (100 mL). The suspension is filtered in an inert manner and the filtrate is concentrated to dryness in a fine vacuum (1 × 10 ^-3 mbar) and the resulting solid is dried in a fine vacuum (1 × 10 ^-3 mbar).

Yield: 2.96 g (17.09 mmol, 64% with respect to [nBu ₄ N] [C ₂ F ₅ BH ₃ ]).
Purity: 99% ( ¹¹ B NMR spectroscopy).

NMR data of C ₂ F ₅ BH ₂ · NCCH ₃ :
¹¹ B NMR (160.46 MHz, CD ₃ CN), δ, ppm: -20.7 (t, ¹ J ( ¹¹ B, ¹ H) = 104.1 Hz).
¹¹ B { ¹ H} NMR (160.46 MHz, CD ₃ CN), δ, ppm: -20.7 (s).
¹⁹ F NMR (470.59 MHz, CD ₃ CN) δ, ppm: -85.2 (m, _CF3, 3F), -125.2 (m, CF _2, 2F).
¹ H NMR (500.13 MHz, CD ₃ CN), δ, ppm: 2.00 (s, CH ₃ CN).
¹ H { ¹¹ B} NMR (500.13 MHz, CD ₃ CN, δ ppm): 1.99 (m, BH ₂ ), 2.00 (s, CH ₃ CN).

Example 24. Reaction of pentafluoroethyldihydridoborane THF adduct with KCN

KCN (130 mg, 2.00 mmol) is initially charged and C ₂ F ₅ BH ₂ .THF (1.0 M in THF, 2.00 mmol, 2.00 ml) added. The reaction mixture is then stirred for 24 h at RT and then for 24 h at 80 ° C and a further 48 h at 110 ° C (bath temperature). More signals at -21.1 ppm anion at -33.6 ppm observed for the [C ₂ F ₅ BH ₂ NC] ^{- -} in the ¹¹ B NMR spectrum, in addition to the signal of the [C ₂ F ₅ CN BH _2] include anion , When increasing the temperature, a decrease in the signal of the species at -21.1 ppm and an increase in signal of [C ₂ F ₅ CN BH _2] is ^- anion was observed. This change reflects the isomerization of [C ₂ F ₅ NC BH _2] ^- anion to [C ₂ F ₅ CN BH _2] ^- anion at higher temperatures.

Example 25. Reaction of pentafluoroethyldihydridoborane THF adduct with AgCN

AgCN (267 mg, 2.00 mmol) is initially charged and treated with C ₂ F ₅ BH ₂ .THF (1 M in THF, 2.00 mmol, 2.00 ml). To ensure exclusion of light, the reaction vessel is wrapped with aluminum foil. The reaction solution is stirred at RT for 24 h. The ¹¹ B NMR spectrum of the reaction mixture, the signal of [C ₂ F ₅ BH ₂ NC] is ^- anion observed at -21.6 ppm.

Example 26: Hydrogenation properties of tetrabutylammonium pentafluoroethyl trihydridoborate

It is presented [n-Bu ₄ N] [C ₂ F ₅ BH ₃ ] (2.0 g, 5.33 mmol) and dissolved in MeOH (15 mL). Then cyclohexanone (1.05 g, 10.6 mmol, 1.1 mL) and methyl orange (~5 mg) are added until a Yellowing is clearly visible. The yellow reaction solution is then treated while stirring with 10% aqueous HCl until the solution turns red with evolution of gas. After 30 minutes, the reaction mixture has turned to yellow-orange, which is why again acidified with 10% aqueous HCl to a red color. The red reaction mixture is stirred for 5 h and the MeOH is then removed on a rotary evaporator. The residue was separated by column chromatography (mobile phase mixture: cyclohexane / ethyl acetate = 2: 1).

By GC-MS, the reduction product cyclohexanol was detected. Retention time GC: 3.25 min, automatic detection of cyclohexanol by the mass spectrometer database.

Example 27: Studies on the electrochemical stability compared to cyanohydridoborates

The electrochemical stability of the perfluoroalkyl (cyano) hydridoborates according to the invention is measured by means of cyclic voltammetry and compared with results for cyanohydridoborates. The measurements are carried out with the device as directed by the manufacturer, as described above.

The working electrode is a glass electrode (3 mm). The reference electrode used is Ag / Ag ⁺ (0.01 M AgNO ₃ in 0.1 M solution of [TBA] [PF ₆ ] / CH ₃ CN). The counter electrode is a platinum wire.

The conductive salt used is tetrabutylammonium hexafluorophosphate ([TBA] [PF ₆ ]) as a 0.1 M solution in acetonitrile (3 mL).

The substance concentration is about 0.0026 M (in 0.1 M solution of [TBA] [PF ₆ ] in acetonitrile). It is measured at a measuring speed of 0.015 V / s. The measuring point rate is 0.005 V.

Table 1 summarizes the results: substance E _pA in V substance E _pA in V [TBA] [BH ₄ ] 0.1 [TBA] [BH ₃ CN] 0.6 [TBA] [C ₂ F ₅ BH ₃ ] 0.7 [TEA] [BH ₂ (CN) ₂ ] 1.1 [EMIM] [C ₂ F ₅ BH ₂ (CN)] 1.6 [BMPL] [C ₂ F ₅ BH ₂ (CN)] 1.6 [TEA] [BH (CN) ₃ ] 2.4 [TEA] [C ₂ F ₅ BH (CN) ₂ ] 2.4

Since the influence of the anions is compared with each other, the anodic potential at the peak (E _pA ) is to be used. The cathodic potential at the peak (E _pK ) is influenced by the cation and is not listed here because it is not the subject of the analysis.

The values for the anodic potential at the peak are readable from the corresponding cyclic voltammograms (abbreviated CVA), which are obtained by the above measuring method. All measurements were made with the same electrode of equal diameter and surface area.

1 to 4 are representative CVAs for the compounds [BMPL] [C ₂ F ₅ BH ₂ (CN)], [TEA] [BH ₂ (CN) ₂ ], [TEA] [C ₂ F ₅ BH (CN) ₂ ] and [TEA ] [BH (CN) ₃ ].

Figure directory

1 is the CVA of [BMPL] [C ₂ F ₅ BH ₂ (CN)].

2 is the CVA of [TEA] [BH ₂ (CN) ₂ ].

3 is the CVA of [TEA] [C ₂ F ₅ BH (CN) ₂ ].

4 is the CVA of [TEA] [BH (CN) ₃ ].

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2004/072089 [0005]
• WO 2012/163489 [0006, 0193]
• WO 2012/163490 [0006]
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• WO 2005/105815 [0007]
• WO 2013/010641 [0007, 0193]
• WO 2006/045405 [0007]
• WO 2011/085966 [0007, 0123, 0134, 0193]
• DE 10128703 A1 [0088]
• EP 76413 [0122]
• EP 40356 [0122]
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Cited non-patent literature

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Claims (12)

Compounds of the formula (I) Cat [(C _n F _{(2n + 1) -m} H _m ) BH _x (CN) _3-x ] (I) where n is an integer from 1 to 12, m is 0, 1, 2, 3 or 4, x is 1, 2 or 3 and Cat is an organic or inorganic cation. Compounds according to Claim 1, in which x denotes 1 or 2, characterized in that the organic cation is selected from ammonium cations of the formula (1), [N (R ⁰ ) ₄ ] ⁺ (1), where R ⁰ is, independently of one another, - H or - OR ¹ , with the condition that in each case only one substituent R ^{0 can} denote OR ¹ , or - N (R ¹ ) ₂ , with the condition that in each case only one substituent R ⁰ N (R ¹ ) _{2 may} mean, or Straight-chain or branched alkyl having 1-20 C atoms, straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, saturated or partially unsaturated cycloalkyl having 3-7 C atoms which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms, Aryl having 6 to 12 carbon atoms which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms, where one or two substituents R ^{0 may be} completely substituted by halogen or one or more substituents R ⁰ partially with halogen, -OR ¹ , -CN, -N (R ¹ ) ₂ , -C (O) OR ¹ , -OC (O) R ¹ , -OC (O) OR ¹ , -C (O) R ^1, -C (O) N (R ¹⁾ _2, -SO ₂ N (R ¹⁾ _2, -C (O) X, -SO ₃ R ^1, -SO ₂ X, -NO _2, -SR ^1, -S (O) R ¹ and / or -SO ₂ R ¹ may be substituted, and wherein one or two non-adjacent and non-α-carbon atoms of the radical R ^{0 are} each independently selected by atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -SO ₂ O-, -C (O) -, -C (O) O-, -N ⁺ (R ¹ ) ₂ - , -P (O) R ¹ O-, -C (O) NR ¹ -, -SO ₂ NR ¹ -, -OP (O) R ¹ O-, -P (O) (N (R ¹ ) ₂ ) NR ¹ -, -P (R ¹ ) ₂ = N- or -P (O) R ¹ - may be replaced, or sulfonium cations of the formula (2) or oxonium cations of the formula (3), [S (R ⁰¹ ) ₃ ] ⁺ (2) or [O (R ⁰¹ ) ₃ ] (3), where R ^{01 are} each independently of one another - straight-chain or branched alkyl having 1-8 C atoms, - unsubstituted aryl having 6 to 30 C atoms or by R ^{1 *} , OR ¹ , SR ¹ , N (R ¹ ) ₂ , CN or halogen-substituted aryl having 6 to 30 C atoms, where, in the case of the sulfonium cations of the formula (2), the substituents R ^{01 can} each independently also be (R ''') ₂ N, or phosphonium cations of the formula (4) [P (R ² ) ₄ ] ⁺ (4), where R ² each independently of one another - N (R ^{1 **} ) ₂ - O (R ^{1 **} ), or - straight-chain or branched alkyl having 1-20 C atoms, - straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, - straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, - saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which is substituted by straight-chain or branched alkyl groups having 1-6 C Atoms, - aryl having 6 to 12 carbon atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms, wherein one or two substituents R ^{2 may be} completely substituted by halogen or may be or several substituents R ^{2 are} partially substituted by halogen, -OR ¹ , -CN, -N (R ¹ ) ₂ , -C (O) OR ¹ , -OC (O) R ¹ , -OC (O) OR ¹ , -C (O) R ¹ , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -C (O) X, -SO ₃ R ¹ , -SO ₂ X, -NO ₂ , -SR ^1, -S (O) R ¹ and / or -SO ₂ R ¹ substituted s one can and, and wherein one or two non-adjacent and non-α-carbon atoms of the radical R ^{2 are} each independently selected by atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, - SO ₂ -, -SO ₂ O-, -C (O) -, -C (O) O-, -N ⁺ (R ¹ ) ₂ -, -P (O) R ¹ O-, -C (O) NR ¹ -, -SO ₂ NR ¹ -, -OP (O) R ¹ O-, -P (O) (N (R ¹ ) ₂ ) NR ¹ -, -P (R ¹ ) ₂ = N- or - P (O) R ¹ - may be replaced and R ^{1 ** are} each independently of one another unsubstituted or partially fluorinated straight-chain or branched C ₁ - to C ₆ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl, or iodonium cations of the formula (5),

wherein the aryl group Ar each independently aryl having 6 to 30 carbon atoms which are unsubstituted or independently of one another by at least one straight-chain or branched alkyl group having 1 to 20 carbon atoms, by at least one straight-chain or branched alkenyl group having 2 to 20 C. Atoms and one or more double bonds, by at least one straight-chain or branched alkynyl group having 2 to 20 C atoms and one or more double bonds, by R ^{1 *} , by NO ₂ , by SR ¹ , by OR ¹ , by N (R ¹ ) ₂ , by CN and / or by halogen or tritylium cations of the formula (6),

where the phenyl groups Ph are unsubstituted or in each case independently of one another by at least one straight-chain or branched alkyl group having 1 to 20 C atoms, by at least one straight-chain or branched alkenyl group having 2 to 20 C atoms and one or more double bonds, by at least one straight-chain or branched one Alkynyl group having 2 to 20 carbon atoms and one or more double bonds, by OR ¹ , by SR ¹ , by N (R ¹ ) ₂ , by CN and / or by halogen may be substituted or uronium cations of the formula (7) or thiouronium cations of Formula (8), [C (NR ³ R ⁴ ) (OR ⁵ ) (NR ⁶ R ⁷ )] ⁺ (7) or [C (NR ³ R ⁴ ) (SR ⁵ ) (NR ⁶ R ⁷ )] ⁺ (8), where R ³ to R ^{7 are} each independently of one another - H or N (R ^{1 *} ) ₂ or - straight-chain or branched alkyl having 1 to 20 C atoms, - straight-chain or branched alkenyl having 2 to 20 C atoms and one or more Double bonds, - straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, - saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms - aryl having 6 to 12 carbon atoms which may be substituted by straight-chain or branched alkyl groups having 1-6 carbon atoms, where one substituent or two substituents of the substituents R ³ to R ^{7 may be} completely substituted by halogen, may or one or more substituents R ^3, R ^4, R ⁶ and R ^{7 may} be partially substituted with halogen, -OR ^1, -CN, -N (R ¹⁾ _2, -C (O) oR ^1, -OC (O) R ¹ , -OC (O) OR ¹ , -C (O) R ¹ , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -C (O) X, -SO ₃ R ¹ , -SO ₂ X, -NO ₂ , -SR ¹ , -S (O) R ¹ and / or -SO ² R ¹ may be substituted, and wherein one or two non-adjacent and non-α-carbon atoms of the radicals R ³ to R ^{7 are} each independently selected from atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -SO ₂ O-, -C (O) -, - C (O) O-, -N ⁺ (R ¹ ) ₂ -, -P (O) R ¹ O-, -C (O) NR ¹ -, -SO ₂ NR ¹ -, -OP (O) R ¹ O-, -P (O) (N (R ¹ ) ₂ ) NR ¹ -, -P (R ¹ ) ₂ = N- or -P (O) R ¹ - may be replaced, or guanidinium cations of the formula (9) [C (NR ⁸ R ⁹ ) (NR ¹⁰ R ¹¹ ) (NR ¹² R ¹³ )] ⁺ (9) where R ⁸ to R ^{13 are} each independently of one another - H, CN, OR ^{1 *} or N (R ^{1 *} ) ₂ , - straight-chain or branched alkyl having 1 to 20 C atoms, - straight-chain or branched alkenyl having 2-20 C- Atoms and one or more double bonds, - straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, - saturated or partially unsaturated cycloalkyl having 3-7 C atoms, with straight-chain or branched alkyl groups having 1-6 C - aryl having 6 to 12 carbon atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 carbon atoms, mean, wherein a substituent or two substituents of the substituents R ⁸ to R ¹³ completely with Halogen, or one or more substituents R ⁸ to R ^{13 may be} partially substituted by halogen, -OR ¹ , -CN, -N (R ¹ ) ₂ , -C (O) OR ¹ , -OC (O) R ¹ , -OC (O) OR ¹ , -C (O) R ¹ , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -C (O) X, -SO ₃ R ^1, -SO ₂ X, -NO ₂ , -SR ¹ , -S (O) R ¹ and / or -SO ₂ R ¹ may be substituted, and wherein one or two non-adjacent and non-α-carbon atoms of the radicals R ⁸ to R ¹³ are each independently replaced by atoms and / or atom groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -SO ₂ O-, -C (O) -, -C (O ) O-, -N ⁺ (R ¹ ) ₂ -, -P (O) R ¹ O-, -C (O) NR ¹ -, -SO ₂ NR ¹ -, -OP (O) R ¹ O-, -P (O) (N (R ¹ ) ₂ ) NR ¹ -, -P (R ¹ ) ₂ = N- or -P (O) R ¹ - may be replaced, or heterocyclic cations of the formula (10) [HetN] ⁺ (10), wherein [HetN] ^{+ is} a heterocyclic cation selected from the group comprising

where the substituents R ^{1 '} to R ^{4' are} each independently of one another - H, - straight-chain or branched alkyl having 1-20 C atoms, which may also be fluorinated or perfluorinated, or - straight-chain or branched alkenyl having 2-20 C- Atoms and one or more double bonds, which may also be fluorinated or perfluorinated, or - represent straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, which may also be fluorinated, - saturated or partially unsaturated cycloalkyl having 3-7 C-atoms, with straight-chain or branched alkyl groups having 1-6 C - aryl having 6 to 12 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms, - saturated, partially or completely unsaturated heteroaryl, heteroaryl-C ₁ -C ₆ - Alkyl or aryl-C ₁ -C ₆ -alkyl, where the substituent R ^{2 '} each independently of one another nor the meaning F, Cl, Br, I, -CN, OR ¹ , -N (R ¹ ) ₂ , -P (O) (R ¹ ) ₂ , -P (O) (OR ¹ ) ₂ , -P (O) (N (R ¹ ) ₂ ) ₂ , -C (O) R ¹ , -C (O) OR ¹ , -C (O) X, -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -SO ₃ R ¹ , -SO ₂ X, -SR ¹ , -S (O) R ^1, -SO ₂ R ¹ and / or NO ₂ in this case may have, on the condition that the substituents R ^{1 ',} R ^3' and R ^{4 'are} independently H and / or straight-chain or branched alkyl having 1 to 20 C atoms and / or straight-chain or branched alkenyl having 2 to 20 C atoms, where the substituents R ^{1 '} , R ^2' , R ^{3 '} and / or R ^4' may together form a ring system, wherein one, two or three substituents R ^{1 '} to R ^4' , but not simultaneously R ^{1 '} and R ^4' , may be completely substituted by halogen or one or more of the substituents R ^{1 '} to R ^{4 '} partially with halogen, -OR ¹ , -CN, -N (R ¹ ) ₂ , -C (O) OR ¹ , -OC (O) R ¹ , -OC (O) OR ¹ , -C (O) R ¹ , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -C (O) X, -SO ₃ R ¹ , -SO ₂ X, -NO ₂ , -SR ¹ , -S (O) R ¹ and / or -SO ₂ R ¹ may be substituted, and wherein one or two non-adjacent and non-α-carbon atoms of the radicals R ^{1 '} to R ^{4' are} each independently selected by atoms and / or atomic groups from the group -O-, -S-, -S (O) -, -SO ₂ -, -SO ₂ O-, -C (O) -, -C (O) O-, -N ⁺ (R ¹ ) ₂ -, -P (O) R ¹ O-, -C (O) NR ¹ -, -SO ₂ NR ¹ -, -OP (O) R ¹ O-, -P (O) (N (R ¹ ) ₂ ) NR ¹ -, -P (R ¹ ) 2 = N- or -P (O) R ¹ - may be replaced and wherein R ^{1 are} each independently H, not or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl, each R ^{1 *} is independently or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl, R '''each independently represents straight-chain or branched alkyl having 1 to 6 C atoms, X is each independently halogen and halogen is F, Cl, Br or I or that the inorganic cation is selected is selected from NO ⁺ , solvated proton [H ⁺ ], a cation of an element of group 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and / or 12 of the periodic table, a complex cation containing at least an element of the group 3, 4, 5, 6, 7, 8, 9, 10, 11 and / or 12 of the periodic table, a cation containing Al, Ga, In, Ge, Sn, Pb, Sb or Bi or a mixture of these cations. Compounds according to claim 1, wherein x is 3, characterized in that the organic cation is selected from ammonium cations of the formula (1), [N (R ⁰ ) ₄ ] ⁺ (1), where R ^{0 is, in} each case independently of one another, - OR ^{1 *} , with the proviso that only one substituent R ^{0 can} denote OR ^{1 *} , or - N (R ^{1 *} ) ₂ , with the proviso that in each case only one substituent R ⁰ N (R ^{1 *} ) ₂ , or - straight-chain or branched alkyl having 1-20 C atoms, - straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, - straight-chain or branched alkynyl with 2 -20 C atoms and one or more triple bonds, - saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms, - aryl having 6 to 12 C atoms Atoms which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms, where one or two substituents R ^{0 can be} completely substituted by halogen or one or more substituents R ⁰ partially with halogen, -OR ^{1 *} , -CN, -N ( R ¹ ) ₂ , -C (O) OR ^{1 *} , -OC (O) R ^{1 *} , -OC (O) OR ^{1 *} , -C (O) R ^{1 *} , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -SO ₂ X, -SR ^{1 *} , -S (O) R ^{1 *} and / or -SO ₂ R ^{1 *} may be substituted, and wherein one or two non-adjacent and non-α-carbon atoms of the radical R ^{0 are} each independently selected by atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -SO ₂ O- , -C (O) -, -C (O) O-, -N ⁺ (R ^{1 *} ) ₂ -, -P (O) R ^{1 *} O-, -C (O) NR ^{1 *} -, -SO ₂ NR ^{1 *} -, -OP (O) R ^{1 *} O-, -P (O) (N (R ¹ ) ₂ ) NR ^{1 *} -, -P (R ^{1 *} ) ₂ = N- or -P ( O) R ¹ - may be replaced, or phosphonium cations of the formula (4), [P (R ² ) ₄ ] ⁺ (4), wherein R ^{2 are} each independently of one another - N (R ^{1 **} ) ₂ , - O (R ^{1 **} ), or - straight-chain or branched alkyl having 1-20 C atoms, Straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms, - aryl having 6 to 12 C atoms which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms, where one or two substituents R ^{2 can be} completely substituted by halogen or one or more substituents R ² partially with halogen, -OR ^{1 *} , -CN, -N (R ¹ ) ₂ , -C (O) OR ^{1 *} , -OC (O ) R ^{1 *} , -OC (O) OR ^{1 *} , -C (O) R ^{1 *} , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -SO ₂ X, -SR ^{1 *} , -S (O) R ^{1 *} and / or -SO ₂ R ^{1 *} can be substituted, and wherein one or two non-adjacent and non-α-carbon atoms of the radical R ^{2 are} each independently represented by atoms and / or at omega-groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -SO ₂ O-, -C (O) -, -C (O) O-, -N ⁺ ( R ^{1 *} ) ₂ -, -P (O) R ¹ O-, -C (O) NR ^{1 *} -, -SO ₂ NR ^{1 *} -, -OP (O) R ^{1 *} O-, -P (O ) (N (R ¹ ) ₂ ) NR ^{1 *} -, -P (R ^{1 *} ) ₂ = N- or -P (O) R ^{1 *} - may be replaced and R ^{1 ** are} each independently or partially fluorinated straight-chain or branched C ₁ - to C ₆ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl, or uronium cations of the formula (7) or thiouronium cations of the formula (8), [C (NR ³ R ⁴ ) (OR ⁵ ) (NR ⁶ R ⁷ )] ⁺ (7) or [C (NR ³ R ⁴ ) (SR ⁵ ) (NR ⁶ R ⁷ )] ⁺ (8), where R ³ to R ^{7 are} each independently - N (R ^{1 *} ) ₂ , or - straight-chain or branched alkyl having 1 to 20 C atoms, - straight-chain or branched alkenyl having 2 to 20 C atoms and one or more double bonds - straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, - saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms, Aryl having 6 to 12 carbon atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms, where one substituent or two substituents of the substituents R ³ to R ^{7 may be} completely substituted by halogen or one or more substituents R ³ , R ⁴ , R ⁶ and R ^{7 are} partially substituted by halogen, -OR ^{1 *} , -CN, -N (R ^{1 *} ) ₂ , -C (O) OR ^{1 *} , -OC (O ) R ^{1 *} , -OC (O) OR ^{1 *} , -C (O) R ^{1 *} , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -SO ₂ X, -SR ^{1 *} , -S (O) R ^{1 *} and / or -SO ₂ R ^{1 *} can be substituted, and wherein one or two non-adjacent and non-α-carbon atoms of the radicals R ³ to R ^{7 are} each independently substituted by atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -SO ₂ O-, -C (O) -, -C (O) O-, -N ⁺ (R ^{1 *} ) ₂ -, -P (O) R ^{1 *} O-, -C (O) NR ^{1 *} -, -SO ₂ NR ^{1 *} -, -OP (O) R ^{1 *} O-, -P (O) (N (R ¹ ) ₂ ) NR ^{1 *} -, -P (R ^{1 *} ) ₂ = N- or -P (O) R ^{1 *} - may be replaced, or guanidinium cations of the formula (9) [C (NR ⁸ R ⁹ ) (NR ¹⁰ R ¹¹ ) (NR ¹² R ¹³ )] ⁺ (9) where R ⁸ to R ^{13 are} each independently of one another - CN, OR ^{1 *} or N (R ^{1 *} ) ₂ , - straight-chain or branched alkyl having 1 to 20 C atoms, - straight-chain or branched alkenyl having 2 to 20 C atoms and one or more double bonds, - straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, - saturated or partially unsaturated cycloalkyl having 3-7 C atoms, with straight-chain or branched alkyl groups having 1-6 C atoms - aryl having 6 to 12 carbon atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 carbon atoms, mean, wherein a substituent or two substituents of the substituents R ⁸ to R ^{13 is} completely substituted by halogen may be or may have one or more substituents R ⁸ to R ^{13 in} part with halogen, -OR ^{1 *} , -CN, -N (R ^{1 *} ) ₂ , -C (O) OR ^{1 *} , -OC (O) R ^{1 *} , -OC (O) OR ^{1 *} , -C (O) R ^{1 *} , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -SO ₂ X, -SR ^{1 *} , -S ( O) R ^{1 *} and / or -SO ₂ R ^{1 *} can be substituted, and wherein one or two non-adjacent and non-α-carbon atoms of the radicals R ⁸ to R ^{13 are} each independently selected from atoms and / or atomic groups of the group -O-, -S-, -S (O) -, -SO ₂ -, -SO ₂ O-, -C (O) -, -C (O) O-, -N ⁺ (R ^{1 *} ) ₂ -, -P (O) R ^{1 *} O-, -C (O) NR ^{1 *} -, -SO ₂ NR ^{1 *} -, -OP (O) R ^{1 *} O-, -P (O) ( N (R ¹ ) ₂ ) NR ^{1 *} -, -P (R ^{1 *} ) ₂ = N- or -P (O) R ^{1 *} - may be replaced, or heterocyclic cations of the formula (10) [HetN] ⁺ (10), wherein [HetN] ^{+ is} a heterocyclic cation selected from the group comprising

where the substituents R ^{1 '} to R ^{4' are} each independently of one another - H, where H is excluded for R ^{1 '} and R ^4' , - denote straight-chain or branched alkyl having 1-20 C atoms, which are also fluorinated or perfluorinated may denote, or denote - straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, which may also be fluorinated or perfluorinated, or - denote straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, which may also be fluorinated, - saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms, - aryl having 6 to 12 carbon atoms, with straight-chain or branched alkyl groups with 1-6 C atoms, saturated, partially or completely unsaturated heteroaryl, heteroaryl-C ₁ -C ₆ -alkyl or aryl-C ₁ -C ₆ -alkyl, in which the substituent R ^{2 'is} each, independently of one another, also the meaning F, Cl, Br, I, -CN, OR ^{1 *} , -N (R ¹ ) ₂ , -P (O) (R ^{1 *} ) ₂ , - P (O) (OR ^{1 *} ) ₂ , -P (O) (N (R ^{1 *} ) ₂ ) ₂ , -C (O) R ^{1 *} , -C (O) OR ^{1 *} , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -SO ₂ X, -SR ^{1 *} , -S (O) R ^{1 *} , and / or -SO ₂ R ¹ may have, under the condition in that the substituents R ^{1 '} and R ^4' in this case independently of one another represent straight-chain or branched alkyl having 1 to 20 C atoms and / or straight-chain or branched alkenyl having 2 to 20 C atoms and in that case the substituent R ^{3 '} independently of the substituents R ^1' and R ^{4 'is} H and / or straight-chain or branched alkyl having 1 to 20 C atoms and / or straight-chain or branched alkenyl having 2 to 20 C atoms, where the substituents R ^1' R ^{2 '} , R ^3' and / or R ^{4 'may} together form a ring system, wherein one, two or three substituents R ^1' to R ^{4 '} , but not simultaneously R ^1' and R ^{4 '} , complete with halo may be substituted or one or more of the substituents R ^{1 '} to R ^4' partially with halogen, -OR ^{1 *} , -CN, -N (R ¹ ) ₂ , -C (O) OR ^{1 *} , -OC (O ) R ^{1 *} , -OC (O) OR ^{1 *} , -C (O) R ^{1 *} , -C (O) N (R ¹ ) ₂ , -SO ₂ N (R ¹ ) ₂ , -SO ₂ X, -SR ^{1 *} , -S (O) R ^{1 *} and / or -SO ₂ R ^{1 *} may be substituted, and wherein one or two non-adjacent and non-α-carbon atoms of the radicals R ^{1 '} to R ^{4' are} each independently by atoms and / or atomic groups selected from the group -O-, -S-, -S (O) -, -SO ₂ -, -SO ₂ O-, -C (O) -, -C (O) O- , -N ⁺ (R ^{1 *} ) ₂ -, -P (O) R ^{1 *} O-, -C (O) NR ^{1 *} -, -SO ₂ NR ^{1 *} -, -OP (O) R ^{1 *} O -, -P (O) (N (R ¹ ) ₂ ) NR ^{1 *} -, -P (R ^{1 *} ) ₂ = N- or -P (O) R ^{1 *} - may be replaced and wherein R ^{1 are} each independently each other for H not or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl, each R ^{1 *} is independently or partially or perfluorinated straight-chain or branched C ₁ - to C ₁₈ -alkyl; C ₃ to C ₇ cycloalkyl; unsubstituted or substituted phenyl, R '''each independently represents straight-chain or branched alkyl having 1 to 6 C atoms, X is each independently halogen and halogen is F, Cl, Br or I or that the inorganic cation is selected is derived from a cation of an element of group 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and / or 12 of the periodic table, a complex cation containing at least one element of group 3, 4, 5, 6, 7, 8, 9, 10, 11 and / or 12 of the Periodic Table, a cation containing Al, Ga, In, Ge, Sn, Pb, Sb or Bi or a mixture of these cations. Compounds according to claim 1, 2 or 3, characterized in that the variable n stands for 2, 3 or 4. Process for the preparation of compounds of the formula (I) according to Claim 1 or 3, in which x is 3 and m is 0, characterized in that a compound of the formula (II) C _n F _{(2n + 1)} Li (II), where n is an integer from 1 to 12, is reacted with a compound of formula (III), BH ₃ · X (III), where X is a coordinating organic molecule which stabilizes the trihydrido-borane complex, the reaction conditions being such that both the water content and the oxygen content are at most 1000 ppm, and optionally subsequently at least one cation exchange with a compound of the formula (IV) CatA (IV), where Cat is another organic or inorganic cation according to claim 1 or 3, and A is an anion selected from Cl ^- , Br ^- , I ^- , [CO ₃ ] ^2- , [R ₁ C (O) O ] ^- , [R ₁ SO ₃ ] ^- , [R ₂ C (O) O] ^- , [R ₂ SO ₃ ] ^- , [R ₁ OSO ₃ ] ^- , [BF ₄ ] ^- , [PF ₆ ] ^- , [(R ₂ ) ₂ P (O) O] ^- or [R ₂ P (O) O ₂ ] ^2- , wherein each R ₁ is independently straight-chain or branched alkyl having 1 to 4 C atoms, R _{2 are} each independently each other straight-chain or branched perfluorinated alkyl having 1 to 4 carbon atoms, wherein the electroneutrality of the salts of the formula CatA is observed. A method according to claim 5, characterized in that the compound of formula (III) is prepared from an alkali metal tetrahydridoborate. Process for the preparation of compounds of the formula (I) according to one or more of Claims 1, 2 or 4, in which x denotes 1, characterized in that a compound of the formula (I) in which x represents 3 corresponds to the formula ( I-1) Cat [(C _n F _{(2n + 1) -m} H _m ) BH ₃ ] (I-1), wherein Cat, n and m have the meaning given in claim 1 or 3, is reacted with a cyanating reagent, the conditions of the reaction being chosen such that the oxygen content is at most 1000 ppm, and optionally subsequently at least one cation exchange with a compound of the formula (IV) CatA (IV), where Cat is another organic or inorganic cation according to claim 1 or 2 and A is an anion selected from Cl ^- , Br ^- , I ^- , [CO ₃ ] ^2- , [R ₁ C (O) O] ^- , [R ₁ SO ₃ ] ^- , [R ₂ C (O) O] ^- , [R ₂ SO ₃ ] ^- , [R ₁ OSO ₃ ] ^- , [BF ₄ ] ^- , [PF ₆ ] ^- , [ HSO ₄ ] ^1- , [NO ₃ ] ^- , [(R ₂ ) ₂ P (O) O] ^- or [R ₂ P (O) O ₂ ] ^2- , wherein each R ₁ is independently straight-chain or branched alkyl 1 to 4 carbon atoms, R ₂ each independently of one another means straight-chain or branched perfluorinated alkyl having 1 to 4 C atoms, wherein the electroneutrality of the salts of the formula CatA is to be observed. Process for the preparation of compounds of the formula (I) according to one or more of Claims 1, 2 or 4, in which x is 1 or 2, characterized in that a compound of the formula (I) in which x represents 3, corresponding to Formula (I-1) Cat [(C _n F _{(2n + 1) -m} H _m ) BH ₃ ] (I-1), where Cat, n and m have the meaning given in Claim 1 or 3, with a compound of the formula (VI) or with a mixture of the acid of the formula (VI) and its salt, RC (O) OH (VI), where R is a straight-chain or branched alkyl group or perfluoroalkyl group having 1 to 6 C atoms, wherein the conditions of the reaction are selected such that the oxygen content is at most 1000 ppm, subsequently the compound of the formula (VIIa) or (VIIb ) Cat [(C _n F _{(2n + 1) -m} H _m ) BH ₂ OC (O) -R] (VIIa), Cat [(C _n F _{(2n + 1) -m} H _m ) BH (OC (O) -R) ₂ ] (VIIb), is reacted with a cyanating reagent without or under microwave irradiation, wherein Cat, n, m and R have one of the meanings mentioned above and wherein the conditions of the reaction are chosen such that both the water content and the oxygen content is at most 1000 ppm, and optionally below at least one cation exchange with a compound of the formula (IV) CatA (IV), where Cat is another organic or inorganic cation according to claim 1 or 2 and A is an anion selected from Cl ^- , Br ^- , I ^- , [CO ₃ ] ^2- , [R ₁ COO] ^- , [R ₁ SO ₃ ] ^- , [R ₂ COO] ^- , [R ₂ SO ₃ ] ^- , [R ₁ OSO ₃ ] ^- , [BF ₄ ] ^- , [PF ₆ ] ^- , [HSO ₄ ] ^1- , [NO ₃ ] ^- , [(R ₂ ) ₂ P (O) O] ^- or [R ₂ P (O) O ₂ ] ^2- , wherein each R ₁ independently of one another represents straight-chain or branched alkyl having 1 to 4 C atoms, R ₂ is independently of one another straight-chain or branched perfluorinated alkyl having 1 to 4 C atoms, wherein the electroneutrality of the salts of the formula CatA is to be observed. Use of compounds of the formula (I) according to one or more of claims 1, 2 or 4 with organic cations as an additive for polymers, solvents or solvent addition, as a catalyst for organic synthesis, as a phase transfer catalyst, as an electrolyte component in electrochemical, electronic or optoelectronic devices, as a fluorine surfactant, as a heat transfer medium, as a release agent, extractant, as a plasticizer, as a lubricant or component of lubricating oils or fats, as a hydraulic fluid or additive for hydraulic fluids. Electrolyte formulation containing at least one compound of the formula (I) according to one or more of claims 1, 2 or 4. Electrochemical or optoelectronic device containing at least one compound of the formula (I) according to one or more of claims 1, 2 or 4. Compounds of the formula (VIIa) or (VIIb) Cat [(C _n F _{(2n + 1) -m} H _m ) BH ₂ OC (O) -R] (VIIa), Cat [(C _n F _{(2n + 1) -m} H _m ) BH (OC (O) -R) ₂ ] (VIIb), wherein R is a straight-chain or branched alkyl group or perfluoroalkyl group having 1 to 10 C atoms, n is an integer from 1 to 12, m is 0, 1, 2, 3 or 4 and Cat is an alkali metal cation or a tetraalkylammonium cation in which the alkyl groups in the tetraalkylammonium cation each independently have 1 to 10 C atoms.

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