CN1990491B - Volatile metal beta-ketoiminate and metal beta-diiminate complexes - Google Patents

Abstract

Volatile metal beta-ketoiminate and metal beta-diiminate complexes are disclosed. The invention provides the metal ketoiminate complexes, and a preparation method and a use method thereof, wherein the complexes contain copper, silver, gold, cobalt, ruthenium, rhodium, platinum, palladium, nickel, osmium, and/or indium, and methods for making and using same are described herein. In certain embodiments, the metal complexes described herein may be used as precursors to deposit metal or metal-containing films on a substrate through, for example, atomic layer deposition or chemical vapor deposition conditions.

Description

Volatile complexes of metal β-ketimine salts and metal β-diimine salts

Cross References to Related Applications

This application claims the benefit of US Provisional Application No. 60/640338, filed December 30,2004. the

Background technique

The semiconductor industry employs metal-containing interconnects, such as copper (Cu), in electronic devices such as, for example, prior art microprocessors. Metallic interconnects can be thin metal wires embedded in a three-dimensional grid through which the millions of transistors at the heart of a microprocessor communicate and perform complex calculations. In these and other applications, since copper is an excellent conductor of electricity, copper or its alloys may be chosen over other metals such as, for example, aluminum, resulting in higher speed interconnects with greater current carrying capability. the

Interconnect pathways in electronic devices are typically fabricated by a damascene process whereby channels and vias in a dielectric insulator that are patterned and etched by photolithography are coated with a thin conformal layer of a diffusion barrier material. Diffusion barrier layers are often used with metal or copper layers to prevent detrimental effects due to interaction or diffusion of the metal or copper layer with other parts of the integrated circuit. Exemplary barrier materials include, but are not limited to, titanium, tantalum, tungsten, chromium, molybdenum, zirconium, ruthenium, vanadium, and/or platinum, and their carbides, nitrides, carbonitrides, silicon carbide, silicon nitride, and carbon Silicon nitride and alloys containing these materials. In some approaches, such as when, for example, the interconnects contain copper, a thin copper "seed" or "strike" can be applied over the diffusion barrier before these features are completely filled with pure copper. layer. In other cases, the copper seed layer may be replaced by or supplemented with a similar cobalt or similar thin film "glue" layer. Subsequently, excess copper can be removed using chemical mechanical polishing. Since the smallest feature to be filled may be less than 0.2 micron wide and more than 1 micron deep, it is preferred to deposit it using a metallization technique that fills these features uniformly without leaving any voids that could lead to electrical failure in the final product Copper seed layer, copper glue layer and/or diffusion barrier layer. the

Various methods such as ionized metal plasma (IMP), physical vapor deposition (PVD), chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma assisted chemical vapor deposition (PACVD), plasma modified Chemical vapor deposition (PECVD), electroplating and electroless coating to deposit metal-containing layers such as metallization layers, diffusion barrier layers and/or other layers. Among them, CVD and ALD methods employing one or more organometallic precursors may be the most promising approaches, as these methods provide excellent phase coverage for high aspect ratio structures with good via-filling characteristics. In a typical CVD process, a vapor of a volatile organometallic precursor containing a desired metal is introduced to the surface of a substrate where a chemical reaction occurs resulting in the deposition of a thin film containing the metal in compound or pure elemental form on the substrate. Since the metal is usually delivered in vapor form as a volatile precursor, the metal can reach both vertical and horizontal surfaces, resulting in an evenly distributed film. In a typical ALD process, volatile organometallic precursor and reagent gases enter the reactor in alternating pulses to deposit self-limiting alternating monolayers of precursor/reagent on a substrate, where the monolayers react together to form a metal film or A metal-containing film that is subsequently reduced to the metal or used in the as-deposited state. For example, if a copper organometallic precursor is reacted with a suitable oxidizing agent in an ALD process, the resulting cuprous oxide or copper oxide monolayer or multilayers can be used in semiconductor applications, or reduced to copper metal. the

For copper thin films, some of the same precursors suitable for CVD and other deposition methods may also be suitable as ALD precursors. In some applications, it may be preferable that the precursors are highly volatile, deposit a substantially pure (i.e., about 95% pure or about 99% pure or higher) copper film, and/or make it possible to cause contamination The amount of species entering the reaction chamber or reaching diffusion barriers or other underlying surfaces is minimized. Also, in these applications, good adhesion between the copper film and the diffusion barrier layer may be preferred, since poor adhesion can lead to delamination of the copper film and other conditions during chemical mechanical polishing. the

In order to deposit low-resistance copper films by the above methods, especially CVD or ALD methods, several organometallic precursors have been developed. Two frequently used and widely studied families of copper organometallic precursors are Cu(I) and Cu(II) precursors. A commonly used Cu(I) precursor is that of the general formula "Cu(I)(hfac)(W)", where "hfac" stands for 1,1,1,5,5,5-hexafluoro- The 2,4-pentanedioxide anion, (W) represents a neutral stable ligand such as, for example, an alkene, an alkyne or a trialkylphosphine. A specific example of a Cu(I) precursor having the above general formula is 1,1,1,5,5,5-hexafluoro-2,4-pentanediolcopper(I)trimethylvinylsilane ( Hereinafter referred to as Cu(hfac)(tmvs)), sold under the trade name CUPRASELECT ^(TM) by Air Products and Chemicals, Inc., Allentown, PA, which is the assignee of the present application. These Cu(I) precursors can deposit films by disproportionation, where two molecules of the precursor react on a heated substrate surface to yield copper metal, two molecules of free ligand (W), and a volatile by-product Cu ^{( +2)} (hfac) ₂ . Equation (1) provides an example of a disproportionation reaction:

(1)2Cu ⁽⁺¹⁾ (hfac)W→Cu+Cu ⁽⁺²⁾ (hfac) ₂ +2W

In CVD deposition, the disproportionation reaction shown in equation (1) typically occurs at about 200°C; however, other temperatures may also be used, depending on the deposition method. As shown in equation (1), Cu ⁽⁺²⁾ (hfac) ₂ constitutes a by-product of this reaction and may need to be removed from the reaction chamber.

Another type of Cu(I) precursor is a precursor of the general formula "(Y)Cu(Z)". In these particular Cu(I) precursors, "Y" is an organic anion and "Z" is a neutral stable ligand such as, for example, a trialkylphosphine. An example of such a precursor is _CpCuPEt3 , where Cp is cyclopentadienyl and _PET3 is triethylphosphine. Under typical CVD conditions, two of these precursor molecules can react at the wafer surface, whereby the two stable trialkylphosphine Z ligands and the copper center dissociate, the two (Y) ligands couple together, and Copper(I) centers are reduced to copper metal. The whole reaction is shown in reaction formula (2).

(2)2(Y)Cu(Z)→2Cu+(Y-Y)+2(Z)

In some cases, however, this type of chemistry can be problematic because the released trialkylphosphine ligands can contaminate the reaction chamber and act as undesired N-type silicon dopants. the

As previously mentioned, another precursor used to deposit copper-containing films is a Cu(II) precursor. Unlike Cu(I) precursors, Cu(II) precursors require the use of an external reducing agent, such as, for example, hydrogen or alcohols, to deposit a substantially impurity-free copper film. An example of a typical Cu(II) precursor has the formula Cu(II)(Y) ₂ , where (Y) is an organic anion. Examples of precursors of this type include, but are not limited to, Cu(II) (β-diketonate), Cu(II) bis(β-diimine) and Cu(II) bis(β-ketimine) ) compounds. Equation (3) provides an example of a deposition reaction in which hydrogen is used as a reducing agent.

(3)Cu(II)(Y) ₂ +H ₂ →Cu+2YH

The Cu(II) precursor is usually a solid, and the temperature required to deposit the film is usually higher than 200 °C. the

Although copper precursors are widely used as interconnects, other metals or alloys are also used as thin films in electronic devices. Examples of these metals include silver (Ag), gold (Au), cobalt (Co), ruthenium (Ru), rhodium (Rh), platinum (Pt), palladium (Pd), nickel (Ni), osmium (Os), Indium (In) and its alloys. the

Contents of the invention

The metal complexes and methods of their preparation and use are described below, such as eg as precursors in deposition methods. In one aspect, the invention provides a metal complex represented by formula (I):

Wherein M is a metal selected from Cu, Au, Ag, Co, Ru, Rh, Pt, In, Pd, Ni and Os;

Wherein X is selected from oxygen and NR ⁵ ;

Wherein, each of R ¹ , R ² , R ³ and R ⁵ is independently selected from a hydrogen atom; a halogen atom; a nitro group of the general formula NO ₂ ; an alkyl group of the general formula C _n H _2n+1 , wherein n is 1 A number of -20; a fluoroalkyl group of the general formula C _n H _x F _y , wherein the sum of (x+y) is equal to the sum of (2n+1), and n is a number from 1 to 20; the general formula is (R ⁶ ) Alkylsilanes of ₃ Si, wherein each of R ⁶ is independently an alkyl, alkoxy or amide containing 1-20 carbon atoms; an aryl group containing 6-12 carbon atoms; containing 6-12 Alkyl-substituted aryl groups of carbon atoms; aryl groups substituted by fluoroalkyl groups containing 6-12 carbon atoms; fluoroaryl groups containing 6-12 carbon atoms; the general formula is (CH ₂ ) _n O(C _m H _2m+1 ) ethers, wherein n and m are independently numbers from 1 to 20; fluoroethers of the general formula (C _n H _x F _y )O(C _m H _w F _z ), wherein (x+y )=2n, (w+z)=(2m+1), n and m are each independently a number from 1 to 20; the general formula is (R ⁷ ) ₃ SiO silyl ethers, wherein each of R ⁷ are independently alkyl groups containing 1-20 carbon atoms or aryl groups containing 6-12 carbon atoms; alkoxy groups containing 1-20 carbon atoms; and amides containing 1-20 carbon atoms;

Wherein R ⁴ is selected from an alkyl group whose general formula is C _n H _2n+1 , wherein n is a number from 1 to 20; a fluoroalkyl group whose general formula is C _n H _x F _y , wherein the sum of (x+y) is equal to The sum of (2n+1), and n is a number from 1 to 20; the general formula is (R ⁶ ) ₃ Alkylsilanes of Si, wherein R ⁶ is each independently an alkyl group containing 1 to 20 carbon atoms, Alkoxy or amide; aryl group containing 6-12 carbon atoms; aryl group substituted by alkyl group containing 6-12 carbon atoms; aryl group substituted by fluoroalkyl group containing 6-12 carbon atoms; containing 6 -A fluoroaryl group with 12 carbon atoms; the general formula is (CH ₂ ) _n O(C _m H _2m+1 ) ether, wherein n and m are independently numbers from 1 to 20; the general formula is (C _n H _x F _y ) O(C _m H _w F _z ) fluoroether, wherein (x+y)=2n, (w+z)=(2m+1), n and m are each independently 1-20 Number; the general formula is (R ⁷ ) ₃ SiO silyl ethers, wherein each R ⁷ is independently an alkyl group containing 1-20 carbon atoms or an aryl group containing 6-12 carbon atoms; containing 1- An alkoxy group of 20 carbon atoms; and an amide containing 1-20 carbon atoms, and wherein ^R is connected to L by removing hydrogen, atom or group;

Wherein L is a ligand selected from the group consisting of: alkyl nitriles containing 2-20 carbon atoms; silyl nitriles of the general formula (R ⁸ ) ₃ SiCN, wherein R ⁸ each independently contains 1-20 Alkyl, alkoxy or amides of carbon atoms; alkynes containing 1-20 carbon atoms; silyl alkynes of the general formula (R ⁹ ) ₃ SiCCR ¹⁰ , wherein R ⁹ each independently contains 1-20 Alkyl, amide or alkoxy of 3 carbon atoms, R ¹⁰ is hydrogen, alkoxy, amide or alkyl containing 1-20 carbon atoms; the general formula is (R ¹¹ ) ₃ SiCCSi(R ¹¹ ) ₃ A silyl alkyne, wherein ^R each independently is an alkyl, amide or alkoxy group containing 1-20 carbon atoms; an alkene, a diene or a triene containing 1-20 carbon atoms; the general formula is ( R ¹² ) ₃ SiCR ¹³ C(R ¹³ ) ₂ silyl olefins, wherein each R ¹² is independently an alkyl, alkoxy, aryl, vinyl or amide containing 1-20 carbon atoms, R ¹³ are each independently hydrogen, an alkyl group containing 1-20 carbon atoms, or an aryl group containing 6-12 carbon atoms; the general formula is (R ¹⁴ ) ₃ SiCR ¹³ CR ¹³ Si(R ¹⁴ ) ₃ Two (silyl) olefins, wherein each R ¹⁴ is independently an alkyl group, an alkoxy group or an amide containing 1-20 carbon atoms, and each R ¹³ is independently a hydrogen atom or contains 1-20 carbon atoms An alkyl group containing 3-20 carbon atoms; a general formula of (R ¹⁵ ) ₂ CCC(R ¹⁵ ) ₂ propadiene, wherein each of R ¹⁵ is independently a hydrogen atom or the general formula is ( R ¹⁶ ) Alkylsilane of ₃ Si, wherein each of R ¹⁶ is independently an alkyl group, amide or alkoxy group containing 1-20 carbon atoms; the general formula is R ¹⁷ NC's alkyl silane, wherein R ¹⁷ is An alkyl group containing 1-20 carbon atoms; the general formula is (R ¹⁸ ) ₃ SiNC silyl isocyanides, wherein each R ¹⁸ is independently an alkyl group containing 1-20 carbon atoms, and contains 6-12 aryl of carbon atoms, and wherein L is connected to ^R by removal of a hydrogen, atom or group; and

wherein the organometallic bond between M and L is selected from two single bonds or one single bond. the

In another aspect, there is provided a method of depositing a metal-containing film on a substrate, comprising: contacting the substrate with a metal complex of general formula (I) above, wherein the contacting is carried out under conditions sufficient to react the complex and form a film. the

In another aspect, there is provided an electronic device comprising a metal-containing film, wherein the film is deposited using a metal complex having the general formula (I) above. the

In yet another aspect, there is provided a method of preparing a metal complex of the general formula (I) above, wherein X is oxygen, comprising: preparing a primary amine of the general formula H ₂ NR ⁴ L, wherein R ⁴ and L are as above said; polycondensation of β-diketones of general formula R ¹ C(O)CHR ² C(O)R ³ and primary amines to form R ¹ C(O)CHR ² CNR ⁴ LR ³ and R ¹ , R ² , R ³ , R ⁴ and L a β-ketimine intermediate as described above, and deprotonating the β-ketimine intermediate with a base in the presence of a metal source to form a metal complex .

In another aspect, there is provided a method of preparing a metal complex of the above general formula (I), wherein X is oxygen, comprising: polycondensing an amine of the general formula H ₂ NR ⁴ and a general formula of R ¹ C(O)CHR ² β ^- diketones ^{of C} ( ^{O )R 3 to form the first} intermediate β-ketimine product; attaching ligand (L) to R ⁴ in this first intermediate β-ketimine product yields a second β-ketimine product of general formula R ¹ C(O)CHR ² CNR ⁴ LR ³ an intermediate β-ketimine product wherein R ¹ , R ² , R ³ , R ⁴ and L are as described above; deprotonating this second β-ketimine intermediate in the presence of a metal source to form metal complexes.

Description of drawings

Figure 1 provides _an exemplary structure _{of one} of the metal complexes described herein, or Cu(MeC(O)CHC( _{NCH2CH2OSiMe2} ( _C2H3 ))Me).

Figure 2 provides another embodiment _{of a} metal complex described herein or _an exemplary structure of Cu(MeC(O)CHC( _{NCH2CH2NMeSiMe2} ( _C2H3 ))Me).

Detailed ways

Metal complexes, particularly copper(I) complexes, and methods of making and using them are described below. Metal complexes can be used, for example, as precursors to deposit metal films or metal-containing films by various deposition methods, including CVD or ALD methods. the

The metal complexes described herein possess one or more advantageous properties due to their unique structures. Compared with other organometallic metal precursors, the metal complexes described herein have both relatively high thermal stability and relatively high chemical reactivity. The combination of these two properties makes them ideal as CVD and ALD precursors, especially Ideal for ALD precursors. Ideally for a CVD system, the precursors react only on the heated substrate surface and not in the delivery vapor and/or process chamber. Ideally for an ALD system, the metal precursors react at specific locations without being affected by undesirable thermal aging in the vapor delivery and/or process chamber. The metal complexes described herein have relatively high thermal stability, which allows them to be delivered as steady-state vapors to CVD or ALD reactors. In this connection mode, we believe that since the ligand L is directly attached to the ketimine or diimine ligand, the ligand is not easy to dissociate from the metal center (M) to become a free molecule, which tends to The coordination relationship between the ligand L and the metal center is maintained under thermal conditions usually sufficient to completely dissociate the ligand L. This is in contrast to similar complexes where L is only bonded to the metal center. In an alternative embodiment, the substituent ^R4 that associates the ketimine or diimine ligand with the ligand L can be chemically engineered such that under correct process conditions this association can be broken or dissociated such that Efficient release of Ligand L. The term "associate" as used herein refers to linking a ketimine or diimine ligand with a ligand L, which can include, but is not limited to, chemical bonds (e.g., covalent bonds, hydrogen bonds, etc.), electrostatic attraction, Lewis acid-Lewis base interactions, and/or other methods. Under these embodiments, and process conditions sufficient to release ligand L, for example, disproportionation of the complex, formation of metal or metal-containing films can be allowed. Moreover, dissociation of ^R4 and ligand L can reduce the precursors to small molecular weight units that are more easily desorbed during processing, for example, in CVD or ALD reactors. For example, if the precursors and water react sufficiently, the dissociation results in the growth of copper oxides and the release of hydrolyzed small molecular weight volatile ligand fragments. For example, the metal complex Cu(Me(C(O)CHC(NCH ₂ CH ₂ NMeSiMe ₂ (C ₂ H ₃ ))Me) (where the C ₂ H ₃ group in the complex represents vinyl) reacts with water to form Solid cuprous oxide, MeC(O)CH ₂ C(NCH ₂ CH ₂ NMeH)Me, and C ₂ H ₃ Me ₂ SiOH, the latter coupling to tetramethyldivinyldisiloxane.

Another unique feature of these complexes is their ability to provide spatial exposure of more metal centers on one face of the precursor. Typical β-ketoimine or β-diketoalkene compounds are flat molecules in which the coordinating diketomate or ketoiminate anion, metal center and olefin are all in the same plane. In contrast, the complexes described here can allow the coordination plane of the complex to become a convex arch, pushing the metal center further down the complex, thereby making it more exposed and more accessible to the surface and reagent molecules. For example, in the exemplary metal complex Cu(Me(C(O)CHC(NCH ₂ CH ₂ OSiMe ₂ (C ₂ H ₃ ))Me), the β-ketoiminate chelating ring is tilted away from the copper olefin coordination The triangle is about 7 degrees, so that the copper is exposed more under the molecule. For some ALD and CVD type methods, this exposure and the resulting spatial access (access) may be important, because it helps to The copper atoms contained therein are adsorbed onto the substrate surface. Moreover, by controlling the nature and length of the ^R4 association ligand L, metal precursors with relatively strained conformations can be developed to provide exposed metal centers. By chemical cleavage or Relatively high reactivity was obtained by releasing the strain by dissociating the linkage of ^R4 to the ligand L. In other words, by tuning the structures of these precursors, it should be possible to construct complexes whose internal strain can be linked by breaking ^R4 Release, drives the decomposition of molecules into small volatile organic units, while providing spatially exposed metal centers for high surface reactivity and metal deposition.

Metal complexes described herein have the following general formula (I):

In the general formula (I), M is a metal selected from Cu, Au, Ag, Co, Ru, Rh, Pt, In, Pd, Ni and Os. In certain embodiments, the metal atom M is copper. In general formula (I), X may be oxygen, thereby forming a ketimine salt complex, or alternatively X may be NR ⁵ , thereby forming a diimide salt complex. In the general formula (I), the substituents R ¹ , R ² , R ³ and R ⁵ are each independently selected from a hydrogen atom; a halogen atom; a nitro group of the general formula NO ₂ ; an alkane of the general formula C _n H _2n+1 A group, wherein n is a number between 1-20; a fluoroalkyl group of the general formula C _n H _x F _y , wherein the sum of (x+y) is equal to the sum of (2n+1), and n is between 1-20 The numbers between; the general formula is (R ⁶ ) ₃ Alkylsilanes of Si, wherein R ⁶ is each independently an alkyl, alkoxy or amide containing 1-20 carbon atoms; containing 6-12 carbon atoms Aryl group containing 6-12 carbon atoms; aryl group substituted by alkyl group containing 6-12 carbon atoms; aryl group substituted by fluoroalkyl group containing 6-12 carbon atoms; fluoroaryl group containing 6-12 carbon atoms; general formula ( _Ethers of _{CH 2} ) _n O( _{C m} H _{2m+1 ) ,} wherein n and m _are independently numbers from 1 to 20; Fluoroethers, wherein (x+y)=2n, (w+z)=(2m+1), and n and m are each independently a number from 1 to 20; a formazan of the general formula (R ⁷ ) ₃ SiO Silyl ethers, wherein R ⁷ each independently is an alkyl group containing 1-20 carbon atoms or an aryl group containing 6-12 carbon atoms; an alkoxy group containing 1-20 carbon atoms; and a group containing 1-20 amides of carbon atoms. In the general formula (I), the substituent R ⁴ is selected from an alkyl group of the general formula C _n H _2n+1 , wherein n is a number from 1 to 20; a fluoroalkyl group of the general formula C _n H _x F _y , wherein The sum of (x+y) is equal to the sum of (2n+1), and n is a number from 1 to 20; the general formula is an alkylsilane of (R ⁶ ) ₃ Si, wherein R ⁶ each independently contains 1- Alkyl, alkoxy or amide with 20 carbon atoms; aryl group with 6-12 carbon atoms; alkyl-substituted aryl group with 6-12 carbon atoms; fluoroalkyl group with 6-12 carbon atoms Substituted aryl groups; fluoroaryl groups containing 6-12 carbon atoms; ethers of the general formula (CH ₂ ) _n O(C _m H _2m+1 ), wherein n and m are independently numbers from 1 to 20; general Fluoroethers of the formula (C _n H _x F _y )O(C _m H _w F _z ), where (x+y)=2n, (w+z)=(2m+1), and n and m each It is independently a number of 1-20; the general formula is a silyl ether of (R ⁷ ) ₃ SiO, wherein R ⁷ is each independently an alkyl group containing 1-20 carbon atoms or containing 6-12 carbon atoms An aryl group containing 1-20 carbon atoms; and an amide containing 1-20 carbon atoms, and wherein R ⁴ is associated with L after removing hydrogen, atom or group. Moreover, in formula (I), L is a ligand selected from the group consisting of: alkyl nitriles containing 2-20 carbon atoms; silyl nitriles of the general formula (R ⁸ ) ₃ SiCN, wherein each of R ⁸ are independently alkyl, alkoxy or amides containing 1-20 carbon atoms; alkynes containing 1-20 carbon atoms; silyl alkynes of the general formula (R ⁹ ) ₃ SiCCR ¹⁰ , wherein each of R ⁹ Each is independently an alkyl group, amide or alkoxy group containing 1-20 carbon atoms, and R ¹⁰ is hydrogen, an alkoxy group, amide or alkyl group containing 1-20 carbon atoms; the general formula is (R ¹¹ ) ₃ SiCCSi(R ¹¹ ) ₃ silyl alkynes, wherein each R ¹¹ is independently an alkyl, amide or alkoxy group containing 1-20 carbon atoms; an alkene, di Alkenes or trienes; the general formula is (R ¹² ) ₃ SiCR ¹³ C(R ¹³ ) ₂ silyl olefins, wherein each of R ¹² is independently an alkyl group, an alkoxy group, an alkoxy group containing 1-20 carbon atoms, Vinyl, aryl or amide, and each R ¹³ is independently hydrogen or an alkyl group containing 1-20 carbon atoms; the general formula is (R ¹⁴ ) ₃ SiCR ¹³ CR ¹³ Si(R ¹⁴ ) ₃ bis( Silyl) alkenes, wherein each R ¹⁴ is independently an alkyl group, an alkoxy group or an amide containing 1-20 carbon atoms, and each R ¹³ is independently a hydrogen atom or a compound containing 1-20 carbon atoms Alkyl; Containing allene of 3-20 carbon atoms; General formula is (R ¹⁵ ) ₂ CCC (R ¹⁵ ) Allene of 2, wherein R ¹⁵ is each independently a hydrogen atom, and the general formula is (R ¹⁶ ) Alkylsilanes of ₃ Si, wherein each of R ¹⁶ is independently an alkyl group, amide or alkoxy group containing 1-20 carbon atoms; the general formula is R ¹⁷ NC's alkyl isocyanide, wherein R ¹⁷ is an alkyl group containing An alkyl group of 1-20 carbon atoms; the general formula is (R ¹⁸ ) ₃ SiNC silyl isocyanide, wherein each R ¹⁸ is independently an alkyl group, amide or alkoxy group containing 1-20 carbon atoms; and an aryl group containing 6-12 carbon atoms, and wherein L is associated with ^R after removing hydrogen, atom or group.

The term "alkyl" as used herein includes linear, branched or cyclic alkyl groups containing 1-20 carbon atoms or 1-10 carbon atoms. Exemplary alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, cyclopentyl, and cyclohexyl. The term "alkyl" also applies to alkyl moieties contained in other groups such as fluoroalkyl, haloalkyl, alkylaryl or arylalkyl. The term "aryl" as used herein includes 6-12 membered carbocyclic rings having aromatic character. Exemplary aryl groups include phenyl and naphthyl. The term "alkyl-substituted aryl" refers to an aryl moiety substituted with an alkyl group. Exemplary alkyl-substituted aryl groups include tolyl and xylyl. The terms "halo" and "halogen" include fluorine, chlorine, bromine or iodine. The term "fluoroalkyl" refers to an alkyl moiety in which one or more hydrogen atoms are replaced by a fluorine halogen atom, which may be partially or fully fluorinated, including those containing 1-20 carbon atoms or 1-10 carbon atoms Linear, branched or cyclic fluorinated alkyl groups. Exemplary fluoroalkyl groups include _{-CF3 , -CF2CF3 , -CH2CF3 , -CF2CFH2 ,} or _{-CH2CF2CF3 .} In certain embodiments, some of the groups discussed herein may be substituted with one or more other elements such as, for example, halogen atoms or other heteroatoms such as O, N, Si or S.

In general formula (I), the substituent R ⁴ is chosen such that it can associate with the ligand L. In addition, the ligand L is selected such that it can associate with ^R4 . It is believed that both the ligand L and the substituent ^R4 have a hydrogen, atom or group removed such that ^R4 and L can associate, thereby allowing the ligand L to attach to the copperimine or diimine ligand of the complex. In this linkage, when L is a silylalkene, one of its bonds can be associated with ^R4 . _An exemplary embodiment _is shown in Figure 1 or Cu(Me(C(O)CHC( _{NCH2CH2OSiMe2} ( _C2H3 ))Me ₎ . In this embodiment, X is oxygen and L has the general formula _H2C = _CHSiMe2 , ^R4 is _OCH2CH2 , ^R3 is hydrogen, ^R1 and ^R2 are both methyl. In another embodiment where X _is ^NR5 , ^R5 and L may be associated. In such an embodiment, both the ligand L and the substituent ^R have a hydrogen, atom or group removed such that R ^and L can associate in the same way R ^and L associate.

In certain embodiments, substituent R ⁴ may also be attached to substituents R ¹ , R ² and/or R ³ . In these embodiments _, when ^{R 1} , R ² and/ ^or R ³ are ^neither hydrogen atoms, halogen atoms, nor nitroNO ^R3 connection.

In certain complex embodiments described herein, X is NR ⁵ and R ⁵ can be any of the groups or atoms described above for R ¹ , R ² or R ³ . In these embodiments, Ligand (L), or another Ligand (L), which may be any of the groups or atoms described above, may also be attached to substituent ^R5 as well as substituent ^R4 . In these embodiments, it is believed that at least one of the ligands L has a valency, eg, available to associate with ^R5 , thereby linking the ligand L to the diimine ligand of the complex. In this or other embodiments, substituent ^R5 may also be attached to any one or all of ^R1 , ^R2 , ^R3 and/or ^R4 to form a ring structure. In the latter embodiment, only when R ¹ , R ² and/or R ³ are neither hydrogen atoms, halogen atoms, nor nitroNO ₂ , or alternatively when R ⁵ is a hydrogen atom, the substituent R ⁵ is connected to R ¹ , R ² and/or R ³ .

In certain embodiments, the substituent ^R4 and/or the optional substituent ^R5 (if X is ^NR5 ) can be adjusted so that the metal center of the ligand L and the adjacent ligand is not its own metal Central coordination. In these embodiments, other complexes such as, but not limited to, dimer, trimer, and tetramer complexes may be formed.

In certain embodiments, any or all of the substituents R ¹ , R ² and R ³ may be independently linked to form a ring structure. In certain embodiments, R ¹ and R ² and/or R ² and R ³ may be independently linked to form a ring structure.

In certain embodiments, the metal complexes described herein may contain fluorine. In these embodiments, any one or all of the substituents R ¹ , R ² , R ³ , R ⁴ and R ⁵ may contain fluorine, such as, for example, fluoroalkyl, fluoroalkyl-substituted aryl, fluoroaryl, Alkyl-substituted fluoroalkyl or fluoroalkyl-substituted fluoroaryl. In an alternative embodiment, the metal complexes described herein do not contain fluorine.

In one embodiment, the ligand L in general formula (I) may be an alkylnitrile such as but not limited to CH ₂ CN or Me ₂ CH ₂ CCN. In this embodiment and the preceding embodiments with respect to L, the group defining the ligand L has hydrogen removed so that it can be associated with ^R4 . In an alternative embodiment, the ligand L of general _formula (I) may be a silylnitrile such as but not limited to _Me2CH2SiCN . In yet another embodiment, the ligand L in general formula (I) may be an alkyne, such as but not limited to _CH2CCMe or _CH2CCH . In another embodiment, the ligand L in general formula (I) may be an alkene, such as but not limited to Me ₃ CCHCH ₂ or Me(CH ₂ ) ₂ CHCH ₂ . In another embodiment, the ligand L in the general formula (I) may be a silyl alkyne of the general formula (R ⁹ ) ₃ SiCCR ¹⁰ or (R ¹¹ ) ₃ SiCCSi(R ¹¹ ) ₃ , such as but not Limited to Me ₃ SiCHCH, Me ₂ CH ₂ SiCHCHSiMe ₃ , (MeO) ₂ CH ₂ SiCHCH ₂ or (EtO) ₂ CH ₂ SiCHCH ₂ . In yet another embodiment, the ligand L of general formula (I) may be an allene, such as but not limited to CHCCCH ₂ or MeCCCMe ₂ . In another embodiment, the ligand L in general formula (I) may be an alkyl isocyanate, such as but not limited to Me ₂ CH ₂ CNC. Throughout the foregoing formula and specification, the term "Me" means methyl, "Et" means ethyl, and "i-Pr" means isopropyl.

In the above general formula (I), the organometallic bond between the metal center and the ligand (L) is either 2 single bonds or 1 single bond. the

In one embodiment, the metal ketimine salt complexes described herein wherein X is oxygen can be synthesized by reacting an amine functionalized with a group L and a β-diketone compound to form a β-ketimine intermediate product. The amine may be, for example, a primary amine of the general formula H ₂ NR ⁴ L, wherein R ⁴ and L may be any of the groups or atoms described above. Non-limiting examples of primary amines having the general formula above include H ₂ NCH ₂ CH ₂ OSiMe ₂ (C ₂ H ₃ ). The β-diketone may be a compound of the general formula R ¹ C(O)CHR ² C(O)R ³ , wherein each of R ¹ , R ² and R ³ may be independently any of the groups or atoms described above. Non-limiting examples of β-diketone compounds having the above general formula are 2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 2,4-hexanedione and 3 , 5-Heptanedione. An example would be the reaction of the amine H ₂ NCH ₂ CH ₂ OSiMe ₂ (C ₂ H ₃ ) and 2,4-pentanedione to form the β-ketimine intermediate MeC(O)CH ₂ C(NCH ₂ CH ₂ OSiMe ₂ (C ₂ H ₃ ))Me. Once the β-ketimine intermediate is prepared, it is deprotonated (ie, the acidic proton is removed) and then complexed with a metal source in the presence of a base to give a complex of general formula (I) above.

四氟硼酸盐时，V是四氟硼酸盐阴离子)。基团R⁵可以或不可以连接有基团L。所得β-二亚胺盐配体二次脱质子化，然后和金属源络合，得到具有上述通式(I)的配合物。  In another embodiment, the metal diimide salt complexes described herein, wherein X is NR ⁵ as described above, can be synthesized by first preparing the β-ketimine intermediate as described above, and then using an alkylating agent such as Triethyloxygen Treatment with tetrafluoroborate or dimethylsulfate and reaction of the resulting compound with R ⁵ NH ₂ wherein R ⁵ is as described above affords the β-diimine salt [R ¹ C(R ⁵ NH) CHR ² C(NR ⁴ L)R ³ ] ⁺ [V] ^- as the second intermediate, where V is the conjugate base of the alkylating agent (e.g., when using triethyloxy

In the case of tetrafluoroborate, V is a tetrafluoroborate anion). The group ^R5 may or may not have a group L attached to it. The obtained β-diimine salt ligand is deprotonated for the second time, and then complexed with a metal source to obtain a complex having the above general formula (I).

The reaction of an amine and a β-diketone compound can be carried out in the presence of a solvent. Suitable solvents include, but are not limited to, individual ethers (e.g., diethyl ether ( _Et2O ), tetrahydrofuran ("THE"), di-n-butyl ether, 1,4-bis alkane or ethylene glycol dimethyl ether); a nitrile (eg CH ₃ CN); or an aromatic compound (eg toluene) or a mixture thereof. In certain embodiments, the solvent is THF. The reaction temperature can range from -78°C to the boiling point of the solvent. The reaction time can be from about 0 hours or immediately to about 48 hours, or from about 4 hours to about 12 hours. In certain embodiments, intermediates can be purified by standard procedures such as distillation, sublimation chromatography, recrystallization, and/or trituration. However, in some embodiments, the reaction of the amine and the β-diketone compound can be carried out without solvent, especially if the resulting β-ketimine intermediate is a liquid.

In certain embodiments, the β-ketimine or β-diimine intermediates up to the final metal complex can be the following three tautomers having the following general formulas (II), (III) or (IV): One or more of the constructs:

In the general formula above, the variables ^R1 , ^R2 , ^R3 , ^R4 , X, and Ligand (L) can each independently be any atom or group described herein.

The intermediate β-ketimine product may require activation prior to reaction with amine or ammonia to give the β-diimine. For example, the intermediate β-ketimine product may first need to be converted from triethyloxy Alkylation with tetrafluoroborate or dimethylsulfate.

Equation (IV) gives an example of one embodiment of the preparation of the metal or Cu(I) ketiminate complexes described herein. In this embodiment, the Cu(I) complex is obtained by deprotonating the β-ketoimine intermediate resulting from the reaction of an amine and a β-diketone compound with one or more bases, or by deprotonating the The β-diimine intermediate product obtained by reacting the amine intermediate with amine or ammonia is deprotonated, and then chelated with Cu(I) to obtain a β-ketimine or β-diimine complex, respectively. A non-limiting example of this reaction is shown in equation (4) below, which shows the preparation of the β-ketimine Cu(I) complex:

Reaction (4)

In reaction formula (4), β-ketimine intermediate product is the compound of general formula (VI), and it reacts with alkali i.e. sodium hydride and copper (I) source i.e. cupric chloride, and makes the compound of general formula (I) Cu(I) complexes and sodium chloride. Other bases that can be used in the above reaction include, but are not limited to, lithium hydride, n-butyllithium, potassium hydride, sodium bis(trimethylsilylamide), lithium diisopropylamide, potassium tert-butoxide, and the like. Other sources of copper(I) that can be used in the above reaction include, but are not limited to, copper(I) bromide, copper(I) iodide, copper(I) trifluoroacetate, copper(I) trifluoromethanesulfonate, benxene ) adducts, copper(I) alkoxide, copper(I) amide, copper(I) acetate, copper(I) phenate, copper(I) acetamide and copper(I) alkoxide. In embodiments where other metal or mixed metal complexes are prepared, the metal source is one or more metal salts containing the desired metal M. Desired yields of metal or Cu(I) complexes may range from about 5% to about 95% of theoretical. In certain embodiments, the final product or metal complex, such as a Cu(I) complex, can be purified by standard procedures such as distillation, sublimation, chromatography, recrystallization, and/or trituration. the

Alternatively, the metal complexes of the present invention can be prepared by first synthesizing other similar metal bis(ketimine) and metal bis(diimine) compounds, and then reacting or reducing them with a metal source. Other alternative routes to the synthesis of these precursors are also possible, such as shown in the non-limiting examples given in the Examples below. the

铜)或者醇铜(例如[CuOt-Bu]₄)发生反应，形成金属或Cu(I)配合物。在又一实施方案中，金属配合物可以在合适的电化学方法中由其组成部分，即β-酮亚胺中间产物和金属原子制备。这些相同合成途径可以用来合成金属二亚胺盐配合物。  In an alternative embodiment, the β-ketimine intermediate can be directly contacted with a metal source, such as arylcopper(I) (e.g.

Copper) or copper alkoxides (such as [CuOt-Bu] ₄ ) react to form metal or Cu(I) complexes. In yet another embodiment, the metal complexes can be prepared from their constituent parts, the β-ketimine intermediate, and the metal atoms in a suitable electrochemical method. These same synthetic routes can be used to synthesize metal diimide salt complexes.

Yet another example of this method is the reaction of ethanolamine (H ₂ NCH ₂ CH ₂ OH) with 2,4-pentanedione to give the first intermediate β-ketimine product MeC(O)CH ₂ C(NCH ₂ CH ₂ OH ) Me. The first intermediate β-ketimine product MeC(O)CH ₂ C(NCH ₂ CH ₂ OH)Me is reacted with chlorodimethylvinylsilane to obtain the second intermediate β-ketimine product MeC(O)CH ₂ C(NCH ₂ CH ₂ OSiMe ₂ (C ₂ H ₃ ))Me. This second intermediate β-ketimine product _is deprotonated and complexed with _copper to give the complex Cu(MeC(O)CHC( _{NCH2CH2OSiMe2} ( _C2H3 ) _Me ).

As noted previously, the metal complexes described herein can be used as precursors for depositing copper-containing films on substrates. Examples of suitable substrates include, but are not limited to, semiconductor materials such as gallium arsenide ("GaAs"), silicon boronitride (BN), and silicon-containing compositions such as crystalline silicon, polycrystalline silicon, amorphous silicon, epitaxially grown silicon, dioxide Silicon (“SiO ₂ ”), silicon carbide (“SiC”), silicon oxycarbide (“SiOC”), silicon nitride (“SiN”), silicon carbonitride (“SiCN”), silicone glass (“OSG”) ”), organofluorosilicate glass (“OFSG”), fluorosilicate glass (“FSG”), and other suitable matrices or mixtures thereof. The substrate may also comprise multiple layers on which films such as for example anti-reflection coatings, photoresists, organic polymers, porous organic and inorganic materials, metals such as copper and aluminum, or diffusion barriers may be applied. The metal complexes can be deposited using any of the techniques described herein or known in the art. Exemplary deposition techniques include, but are not limited to, chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma assisted chemical vapor deposition (PACVD), and plasma modified chemical vapor deposition (PECVD).

In certain embodiments, these complexes can be used to form thin films of metals or alloys thereof by CVD or ALD with appropriate reagents. In an alternative embodiment, the metal complex can react via a disproportionation reaction to provide a metal film or a metal-containing film. In another embodiment, the metal complex can be reacted in the presence of a reducing agent to give a metal film or a metal-containing film. For example, in one embodiment, reaction with a halogen source reagent can form a film of a metal halide, while in another embodiment, reaction with a suitable oxidizing agent such as water vapor can provide a metal oxide film. In another embodiment, reaction with an oxidizing agent followed by a reducing agent such as hydrogen can form a metal film or a mixed metal/metal oxide film. Alternatively, the copper precursor may react with a reagent gas activated by a plasma directly from or located downstream from a remote plasma source. The metal complexes disclosed herein can also be used in combination with other metal precursors to form metal thin films, metal-containing thin films and/or metal alloy films. These films can be used in the as-deposited state, or alternatively can be reduced to the desired metal with a suitable reducing agent. the

In certain embodiments, the metal complexes are deposited on the substrate using CVD or ALD techniques. The deposition of the Cu(I) complex may be performed at a temperature of 400°C or below, or 200°C or below, or 100°C or below. In a typical CVD deposition method, a metal complex of general formula (I) is introduced into a reaction chamber, such as a vacuum chamber. In some embodiments, other chemical agents other than the metal complex may be introduced before, during and/or after the introduction of the metal complex. An energy source, such as, for example, thermal energy, plasma energy, or other energy source, energizes the metal complex and optionally chemical reagents to form a film on at least a portion of the substrate. the

As noted previously, in certain embodiments, chemical reagents may be introduced before, during, and/or after introducing the metal complex into the reaction chamber. The choice of chemical reagents can depend on the desired composition of the final membrane. For example, in one embodiment, reaction with a halogen-containing chemical may form a film of a metal halide, but in another embodiment, reaction with an oxidizing chemical may form a metal oxide film. Exemplary chemical agents include, but are not limited to, oxidizing agents (i.e., _O2 , NO, _NO2 , _O3 , CO, CO2 _{, etc.} ); water; halides; halogen-containing silanes; alkylchlorosilanes, alkylbromosilanes, or Alkyl iodosilanes; silicon halide compounds, such as silicon tetrachloride, silicon tetrabromide, or silicon tetraiodide; halogenated tin compounds, such as alkylchlorostannanes, alkylbromostannananes, or alkyliodostannanes; germanium alkane compounds, such as alkylchlorogermane, alkylbromogermane or alkyliodogermane; boron trihalide compounds, such as boron trichloride, boron tribromide or boron triiodide; aluminum halide compounds, such as chloride aluminum, aluminum bromide, or aluminum iodide; alkylaluminum halides; gallium halides such as gallium trichloride, gallium tribromide, or gallium triiodide; or combinations thereof. It is also contemplated that derivatives of the above compounds may also be used. These chemical reagents can be delivered directly to the reaction chamber in gaseous form, in volatile liquid form, sublimated solid form and/or by an inert carrier gas into the reaction chamber. Examples of inert carrier gases include nitrogen, hydrogen, argon, xenon, and the like.

In some embodiments, a metal film can be formed on the surface of a substrate through a disproportionation reaction, such as the Cu(I) complex shown in equation (5) below. the

Reaction 5

In another embodiment, a metal film can be deposited on the surface of a substrate in the presence of a reducing agent, for example, to reduce the film to a metal. Metal complexes of general formula (I) can be introduced into a CVD or ALD reactor together with a reducing agent. The reducing agent is usually introduced in gaseous form. Examples of suitable reducing agents include, but are not limited to, hydrogen gas, alcohols, hydrogen plasma, remote hydrogen plasma, silanes (i.e., diethylsilane, ethylsilane, dimethylsilane, phenylsilane, silane, disilane, aminosilanes), boranes (ie borane, diborane), alanes, germanes, hydrazines, ammonia or mixtures thereof. the

In certain embodiments, metal films are deposited from Cu(I) complexes of general formula (I) by ALD deposition methods. In a typical ALD process, one or more gaseous or vaporous precursors are introduced in alternating pulses during a process cycle into a process chamber containing a substrate. Preferably no more than about one monolayer of material is formed per process cycle by adsorption and preferably by chemisorption. The number of processing cycles used to grow the layer depends on the desired thickness, but can typically exceed 1000 cycles. For semiconductor devices, the process cycle is repeated until the thickness of the barrier or seed layer in the dual damascene structure is sufficient to perform its desired function. the

In the ALD process, the temperature of the substrate is set in a range that facilitates chemisorption, that is, low enough to maintain the bond between the adsorbed species and the underlying substrate unaffected while high enough to avoid The required surface reactions of the cycle provide sufficient activation energy. The processing chamber temperature may be from 0°C to 400°C, or from 0°C to 300°C, or from 0°C to 275°C. The pressure in the process chamber in the ALD process may be 0.1-1000 Torr, or 0.1-15 Torr, or 0.1-10 Torr. However, it should be understood that the temperature and pressure may vary for any particular ALD process, depending on the precursor or precursors involved. the

Any of the foregoing film-forming methods described herein and other film-forming methods known in the art may be used alone or in combination. For example, in one embodiment, a mixed composition copper-containing film may be formed by sequentially depositing a copper oxide film and a copper metal film and then reducing the multiple layers to a pure copper film. the

In certain embodiments, the metal complexes described herein can be dissolved in a suitable solvent to form a solution, such as an amine (e.g., triethylamine), an ether (e.g., THF), an aromatic (e.g., toluene), or any Other solvents disclosed herein. The resulting solution can be flashed in a direct liquid injection (DLI) system and delivered as a vapor to an ALD or CVD reactor chamber. In other embodiments, the complexes described herein can be dissolved in stable liquids such as alkenes or alkynes prior to introduction into the DLI system. the

Example

In the following examples, HP 5890 series 11G.C and 5972 series mass selective detectors equipped with HP-5MS were used to measure the GCMS spectrum of the sample. NMR analysis of the samples was performed with a Bruker AMX500 spectrometer at 500 MHz. The chemical shifts are set by C ₆ D ₆ , 7.16 ppm for 1H and 128.39 parts per million (ppm) for ¹³ C. X-ray analysis was performed using a Bruker D8 platform diffractometer equipped with an APEX CCD detector and a Kryoflex cryostat.

Example 1: Synthesis of H ₂ NCH ₂ CH ₂ OSiMe ₂ (C ₂ H ₃ )

80.0 ml (0.57 mol) of chlorodimethylvinylsilane and 79.0 ml (0.57 mol) of triethylamine were mixed together with 2.0 liters of dry hexane and vigorously stirred at room temperature under a nitrogen atmosphere. 35.0 ml ethanolamine (0.57 mol) was slowly added over a period of 1 hour to give a white viscous slurry. The solid triethylamine hydrochloride was filtered off under nitrogen and washed with an additional 1.0 liter of dry hexane. Hexane was then distilled from the product at atmospheric pressure to yield 58.0 g (70%) of product. The NMR result of product is as follows:

¹ H NMR: (5O0MHz, C ₆ D ₆ ): δ=0.15(d, 6H), δ=2.8(q, 2H), δ=3.5(t, 2H), δ=5.75(dd, 1H), δ =5.94(dq, 1H), δ=6.17(dq, 1H).

Example 2: Synthesis of MeC(O)CH ₂ C(NCH ₂ CH ₂ OSiMe ₂ (C ₂ H ₃ ))Me

58.3 g (0.40 mol) H ₂ NCH ₂ CH ₂ OSiMe ₂ (C ₂ H ₃ ) was slowly added dropwise to 250 ml THF at room temperature in the presence of excess sodium sulfate and under stirring, wherein the THF contained 40 g ( 0.40 mol) of 2,4-pentanedione. The mixture was stirred for 4 hours, then the THF was stripped under vacuum. The residue was then distilled at 120 °C/20 mTorr to give 35 g of the final product (43% yield). The NMR result of product is as follows:

¹ H NMR: (500MHz, C ₆ D ₆ ): δ=0.15(s, 6H), δ=1.40(s, 3H), δ=2.0(s, 3H), δ=2.8(q, 2H), δ =3.27(q, 2H), δ=4.9(s, 1H), δ=5.75(m, 1H), δ=5.95(m, 1H), δ=6.1(m, 1H).

Example 3: Synthesis of Cu(MeC(O)CHC(NCH ₂ CH ₂ OSiMe ₂ (C ₂ H ₃ ))Me)

Dissolve 17.0 g (0.075 mol) of MeC(O)CH ₂ C(NCH ₂ CH ₂ OSiMe ₂ (C ₂ H ₃ ))Me in 10.0 ml of dry tetrahydrofuran (THF) solvent under nitrogen atmosphere over a period of 1 h Add 2.5 g (40% excess, 1.04 mol) of sodium hydride in 100 ml of dry THF under stirring, and stir overnight at room temperature. The mixture was filtered under nitrogen and then slowly added to 7.5 g (0.075 mol) of copper(I) chloride stirred in 10 ml of dry THF at 0° C. under nitrogen over a period of 1 hour and the mixture was subsequently heated to room temperature and stirred overnight. The THF was then stripped off under vacuum and added to 500 ml of dry deoxygenated hexane and stirred for 10 minutes before filtration. After stripping the hexane under vacuum, the crude product was obtained as light blue crystals in a yield of 15.8 g (73%). After sublimation at 20 mTorr and 70°C, an almost colorless crystalline sublimate with a melting point of 72.5°C was obtained. The sublimated crystals were subjected to X-ray analysis and the final structure is shown in Figure 1. The NMR result of product is as follows:

¹ H NMR: (500MHz, C ₆ D ₆ ): δ=0.10(d, 6H), δ=1.53(s, 3H), δ=2.14(s, 3H), δ=3.1(bs, 1H), δ =3.35(bs, 1H), δ=3.55(bs, 1H), δ=3.65(dd, 1H), δ=3.72(bs, 1H), δ=3.83(dd, 1H), δ=4.1(dd, 1H), δ=4.96(s, 1H); ¹³ CNMR: (500 MHz, C ₆ D ₆ ): δ=-2.8(s, 1C), δ=0.3(s, 1C), δ=22.5(s, 1C), δ=27.9(s, 1C), δ=57.1(s, 1C), δ=65.3(s, 1C), δ=79.8(s, 1C), δ=83.2(s, 1C), δ= 98.3(s, 1C), δ=169.2(s, 1C), δ=181.4(s, 1C).

Example 4: Alternative synthesis of Cu(MeC(O)CHC(NCH ₂ CH ₂ OSiMe ₂ (C ₂ H ₃ ))Me)

This synthesis proceeds in two parts:

Part (a): Synthesis of MeC(O)CH ₂ C(NCH ₂ CH ₂ OH)Me

Slowly add 100.0 g (1.0 mol) of 2,4-pentanediol into 600 ml of vigorously stirred hexane, wherein the hexane contains 61.0 g (1 mol) of ethanolamine and 100 g of sodium sulfate drying agent. The mixture eventually became a solid mass and the hexane layer was decanted. 600 ml of THF were then added and the mixture was heated slowly with stirring until all solids except sodium sulfate had dissolved. The THF layer was then poured off and cooled slowly overnight to crystallize. The liquid layer was then decanted and the solid was blotted dry. The yield was 87 g or 61%. NMR results show that it is an intermediate product:

¹ H NMR (500MHz, C ₆ D ₆ ): δ=1.41(s, 3H), δ=2.0(s, 3H), δ=2.76(q, 2H), δ=3.33(t, 2H), δ= 4.83(s, 1H), δ=11.15(bs, 1H).

Part (b): Synthesis of Cu(MeC(O)CHC(NCH ₂ CH ₂ OSiMe ₂ (C ₂ H ₃ ))Me)

Dissolve 40g (0.28mol) of MeC(O)CH ₂ C(NCH ₂ CH ₂ OH)Me in 500ml of dry THF under a nitrogen atmosphere, slowly add it to 250ml of THF and stir in 1 hour 6.7g (0.28mol) of sodium hydride. It was found that hydrogen gas was formed and the mixture became a white viscous slurry. 112 ml of 2.5M n-butyllithium (0.28 mol) were added over a period of 1 hour, at which point 250 ml of additional THF were added for better mixing. The resulting pale yellow suspension was stirred for two more hours, then 33.6 g (0.28 mol) of chlorodimethylvinylsilane were added over a period of 30 minutes and the mixture was stirred for a further 2 hours. This viscous suspension was then added dropwise over a period of 1 hour to 50 ml of dry THF under stirring at 0° C. and containing 29 g (0.28 mol) of copper(I) chloride under a nitrogen atmosphere. The mixture was then warmed to room temperature and stirred overnight. The THF was then stripped off under vacuum, 500 mL of dry hexane was added under a nitrogen atmosphere, the mixture was stirred for 10 minutes, and the hexane was filtered from the solid. An additional 500 ml of hexane was added to the solid, heated to 45°C and stirred for 45 minutes, then filtered and combined with the first extraction of hexane. The hexane was stripped off under vacuum to give 52.0 g of crude light blue crystalline product with a percent yield of 64%. The crude product was then purified by sublimation at 70 °C and 20 mTorr.

Example 5: Synthesis of MeC(O)CH ₂ C(NCH ₂ CH ₂ NMeH)Me

In 30 minutes, 20.0 g (0.2 mol) of 2,4-pentanediol was added dropwise to 200 ml of THF under stirring, which contained 14.8 g (0.2 mol) of N-methylethylene Diamine and 36g sodium sulfate desiccant. The mixture turned yellow and was stirred at room temperature for 2 days. The THF layer was then decanted and kept overnight over dry 2A molecular sieves before stripping the THF under vacuum to give a golden brown oil. The yield was 25.5 g or 82%. The NMR result of product is:

¹ H NMR (500MHz, C ₆ D ₆ ): δ=1.45(s, 3H), δ=2.03(s, 3H), δ=2.05(s, 3H), δ=2.25(t, 2H), δ= 2.74(q, 2H), δ=4.88(s, 1H), δ=11.1(bs, 1H).

Example 6: Synthesis of MeC(O)CH ₂ C(NCH ₂ CH ₂ NMeSiMe ₂ (C ₂ H ₃ ))Me

51.0 g (0.327 mol) of MeC(O)CH ₂ C(NCH ₂ CH ₂ NMeH)Me was added to 1 liter of dry THF stirred under nitrogen atmosphere over a period of 1 hour to give a cream colored viscous suspension , wherein the THF contains 13.1 g (0.327 mol) of potassium hydride. To this was added 45 ml (0.327 mol) of chlorodimethylvinylsilane over a period of 30 minutes, and stirring of the mixture was continued for 2 hours. The THF was then stripped under vacuum and 1 L of dry hexane was added and stirred for 10 minutes. The suspension was then filtered and the solid was washed 3 times with 50 ml additional hexane. All hexane washes were combined and stripped to give 62.3 g, or 80% yield, of a golden brown oil which was then vacuum distilled at 120°C and 20 mTorr. The NMR result of the product is:

¹ H NMR (500MHz, C ₆ D ₆ ): δ=0.18(s, 6H), δ=1.44(s, 3H), δ=2.04(s, 3H), δ=2.24(s, 3H), δ= 2.57(t, 2H), δ=2.71(q, 2H), δ=4.9(s, 1H), δ=5.7(dd, 1H), δ=5.94(dd, 1H), δ=6.2(dd, 1H ), δ=11.1(bs, 1H).

Example 7: Synthesis of Cu(MeC(O)CHC(NCH ₂ CH ₂ NMeSiMe ₂ (C ₂ H ₃ ))Me)

6.1 g (0.025 mol) of MeC(O)CH ₂ C(NCH ₂ CH ₂ NMeSiMe ₂ (C ₂ H ₃ ))Me were added to 175 ml of dry THF with stirring under nitrogen atmosphere over a period of 30 min. and stirred for 2 hours, wherein the THF contained 1.02 g (0.025 mol) of potassium hydride. The slightly cloudy solution was then filtered and added dropwise over a period of 3 hours to 10 ml of dry THF containing 2.5 g (0.025 mol) of copper(I) at 0° C. under a nitrogen atmosphere with constant stirring. in chloride. The mixture was then warmed to room temperature overnight. The THF was then stripped under vacuum, then 200 ml of dry hexane were added under a nitrogen atmosphere, the mixture was stirred for 5 minutes and then filtered. The hexane was stripped to give 6.3 g of the crude product as pale green crystals, or 83% yield, which was then purified by sublimation at 75°C and 20 mTorr. The melting point of the product was 86°C. The sublimated crystals were analyzed by X-rays, and the results are shown in Figure 2. The NMR result of product is as follows:

1H NMR: (500MHz, C ₆ D ₆ ): δ=0.05(bs, 6H), δ=1.65(s, 3H), δ=2.16(s, 3H), δ=2.27(s, 3H), δ= 2.47(bs,1H), δ=2.76(bs,1H), δ=3.11(bs,1H), δ=3.21(bs,1H), δ=3.78(dd,1H), δ=4.0(dd,1H ), δ=4.21(dd, 1H), δ=5.01(s, 1H); and ¹³ CNMR: (500 MHz, C ₆ D ₆ ): δ=-0.05(bs, 1C), δ=-2.5(bs , 1C), δ=23.4(s, 1C), δ=27.9(s, 1C), δ=34.9(s, 1C), δ=51.6(s, 1C), δ=53.0(s, 1C), δ =81.2(s, 1C), δ=84.1(s, 1C), δ=170.1(s, 1C), δ=180.8(s, 1C).

Example 8: Alternative synthesis of Cu(MeC(O)CHC(NCH ₂ CH ₂ NMeSiMe ₂ (C ₂ H ₃ ))Me)

1.625 g (0.0104 mol) of MeC(O)CH ₂ C(NCH ₂ CH ₂ NMeH)Me was added to 0.417 g (0.0104 mol) stirred in 100 ml of dry THF over a period of 30 minutes under nitrogen atmosphere for hydrogenation Potassium, a white viscous paste was obtained. To this was added 4.2 ml of 2.5M n-butyllithium (0.0104 mol) over a period of 5 minutes to give a clear yellow/orange solution. 1.4 ml of chlorodimethylvinylsilane (0.01 mol) was added to the solution. The mixture became cloudy at this point and was stirred for an additional 20 minutes. The resulting slurry was then added dropwise over a period of 30 minutes to 5 ml of dry THF under a nitrogen atmosphere, wherein the THF was at 0° C. and stirred with 1.04 g (0.0104 mol) of copper(I) chloride, then heated to room temperature and Stir overnight. The THF was stripped under vacuum and 100 mL of dry hexane was added under nitrogen atmosphere. The mixture was filtered and then stripped of hexane to give _the crude product _, or Cu(MeC(O)CHC( _{NCH2CH2NMeSiMe2} ( _C2H3 ))Me), which was identified from GCMS _.

Claims (3)

1. Metal complexes selected from the group consisting of: Cu( _MeC ( _O )CHC( _{NCH2CH2OSiMe2} ( _C2H3 )) _Me ); and Cu( _MeC (O)CHC( _{NCH2CH2NMeSiMe2} ( _C2H3 )) _Me ) _. 2. Cu(MeC( _O )CHC( _{NCH2CH2OSiMe2 ( C2H3} )) _Me ). 3. Cu ₍ MeC( _O )CHC( _{NCH2CH2NMeSiMe2} ( _C2H3 ))Me) _.