DE1593565C - Process for the production of new oxygen complexes of zero-valent nickel - Google Patents
Process for the production of new oxygen complexes of zero-valent nickelInfo
- Publication number
- DE1593565C DE1593565C DE19661593565 DE1593565A DE1593565C DE 1593565 C DE1593565 C DE 1593565C DE 19661593565 DE19661593565 DE 19661593565 DE 1593565 A DE1593565 A DE 1593565A DE 1593565 C DE1593565 C DE 1593565C
- Authority
- DE
- Germany
- Prior art keywords
- nickel
- oxygen
- triphenylphosphine
- zero
- electron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 40
- 229910052759 nickel Inorganic materials 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000002926 oxygen Chemical class 0.000 title claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- -1 cycloaliphatic Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000003574 free electron Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical group C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 2
- 230000009918 complex formation Effects 0.000 claims 2
- 229910001882 dioxygen Inorganic materials 0.000 claims 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 150000002815 nickel Chemical group 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 230000002269 spontaneous effect Effects 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- UYLRKRLDQUXYKB-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UYLRKRLDQUXYKB-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000723347 Cinnamomum Species 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical compound C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 2
- 235000017803 cinnamon Nutrition 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 235000021286 stilbenes Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WHSDAOPXSDERMO-UHFFFAOYSA-N C1C[Ni]1.C1CCC(CC1)P(C1CCCCC1)C1CCCCC1.C1CCC(CC1)P(C1CCCCC1)C1CCCCC1 Chemical group C1C[Ni]1.C1CCC(CC1)P(C1CCCCC1)C1CCCCC1.C1CCC(CC1)P(C1CCCCC1)C1CCCCC1 WHSDAOPXSDERMO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- ZOLLIQAKMYWTBR-RYMQXAEESA-N cyclododecatriene Chemical compound C/1C\C=C\CC\C=C/CC\C=C\1 ZOLLIQAKMYWTBR-RYMQXAEESA-N 0.000 description 1
- 208000001848 dysentery Diseases 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- AANJINLZXYSHJP-UHFFFAOYSA-N nickel tri(piperidin-1-yl)phosphane Chemical compound [Ni].C1CCN(CC1)P(N1CCCCC1)N1CCCCC1.C1CCN(CC1)P(N1CCCCC1)N1CCCCC1 AANJINLZXYSHJP-UHFFFAOYSA-N 0.000 description 1
- KFBKRCXOTTUAFS-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 KFBKRCXOTTUAFS-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WWVNWQJKWKSDQM-UHFFFAOYSA-N triethylarsane Chemical compound CC[As](CC)CC WWVNWQJKWKSDQM-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- BPLUKJNHPBNVQL-UHFFFAOYSA-N triphenylarsine Chemical compound C1=CC=CC=C1[As](C=1C=CC=CC=1)C1=CC=CC=C1 BPLUKJNHPBNVQL-UHFFFAOYSA-N 0.000 description 1
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
Es sind bereits Verfahren zur Herstellung von 25 verbindungen der Elemente der V. Hauptgruppe, Komplexen von Übergangsmelallen und Elektronen- d. h. von Stickstoff, Phosphor, Arsen und Antimon donatoren bekannt. und Amide der phosphorigen Säure eingesetzt. Bei-There are already processes for the production of 25 compounds of the elements of the V main group, Complexes of transition melals and electron d. H. of nitrogen, phosphorus, arsenic and antimony donors known. and amides of phosphorous acid are used. At-
Aus Mem. Inst. Sei. fnd. Res. Osaka Univ. 23 (1966), spielsweise: Triphenylphosphin, Tricyclohexylphos-S. 69 und 70, referiert in Chemical Abstracts 65 (1966) phin, Triisopropylphosphin, Triäthylphosphin, Phos-4706 e, f, sowie Nippon Kagaku Zaski 87 (1966) 30 phorigsäuretridiäthylamidjPhosphorigsäuretrimorpho-S. 610 bis 613, referiert in Chemical Abstracts, 65 lid, Triphenylarsin, Triäthylarsin, Triphenylstibin, (1966) 14 485 d bis f ist die Herstellung von Platin- Tripropylstibin.From Mem. Inst. Sei. fnd. Res. Osaka Univ. 23 (1966), for example: triphenylphosphine, tricyclohexylphos-S. 69 and 70, reported in Chemical Abstracts 65 (1966) phin, triisopropylphosphine, triethylphosphine, Phos-4706 e, f, and Nippon Kagaku Zaski 87 (1966) 30 phorigsäuretridiäthylamidjPhosphorigsäuretrimorpho-S. 610 to 613, reported in Chemical Abstracts, 65 lid, triphenylarsine, triethylarsine, triphenylstibine, (1966) 14 485 d to f is the production of platinum tripropylstibine.
bzw. Palladium-Phosphin-Sauerstoffkomplexen be- Als Verbindungen mit π-Elektronensystemen kom-or palladium-phosphine-oxygen complexes as compounds with π-electron systems
kannt. men solche in Frage, die CC-, CO-, CN-Mehrfach-knows. men in question, the CC, CO, CN multiple
Es wurde nun gefunden, daß man Komplexe von 35 bindungen sowie deren Kombination zu konjugierten nullwertigem Nickel, die Sauerstoff als Liganden ent- Mehrfachbindungen enthalten, und deren Derivate, halten, herstellen kann. Dies war überraschend, da Als Beispiele seien genannt: Äthylen, Cyclooctadienbekanntlich die VIII. Gruppe des Periodensystems, (1,5), Cyclododecatrien-(1,5,9), Phenylacetylen, Tolan, in der sich 9 Metalle befinden, eine Sonderstellung Stilben, Cyclododecin, Benzaldehyd, Acrolein, Zimteinnimmt. Es ist auch bekannt, daß alle 9 Metalle von- 40 aldehyd, Acrylnitril, Acrylsäureester, Sorbinsäureeinander sehr unterschiedliche Reaktionen geben ester, Butadiencarbonsäureester, Maleinsäureanhydrid, können. Zwar befinden sich die Metalle Palladium Die nullwertigen Metalle können auch in Komplexen und Platin in derselben senkrechten Kolonne wie das gebunden sein, in denen sowohl Elektronendonatoren Nickel, jedoch in jeweils anderen waagerechten der oben zuerst genannten Gruppe, als auch solche Gruppen. Außerdem ist ein Rückschluß von Metallen 45 der 2. Gruppe gebunden sind.It has now been found that complexes of 35 bonds and their combinations can be conjugated zero-valent nickel containing oxygen as ligands and multiple bonds and their derivatives, can hold, produce. This was surprising because the following examples may be mentioned: ethylene and cyclooctadiene are known the VIII. group of the periodic table, (1,5), cyclododecatriene (1,5,9), phenylacetylene, tolane, in which there are 9 metals, stilbene, cyclododecine, benzaldehyde, acrolein, cinnamon occupy a special position. It is also known that all 9 metals are composed of aldehyde, acrylonitrile, acrylic acid ester, sorbic acid very different reactions give ester, butadiene carboxylic acid ester, maleic anhydride, be able. Although the metals are palladium, the zero-valent metals can also be in complexes and platinum bound in the same vertical column as that, in which both electron donors Nickel, but in each other horizontal group of the above group, as well as such Groups. In addition, an inference of metals 45 of the 2nd group is bound.
oder Elementen mit höherer Atomzahl auf solche mit Als Beispiel für einen nullwertigen Metallkomplexor elements with a higher atomic number to those with As an example of a zero-valent metal complex
niederer Atomzahl selten, wenn nicht überhaupt nicht, mit verschiedenen Elektronendonatoren sei Cyclomöglich bzw. üblich. Darüber hinaus ist bekannt, daß octadien-nickel-(0)-bis-(triphenylphosphin)s Bis-triphebeispielsweise das Nickel eine ganz besondere Stellung nylphosphin-nickel-(0)-äthylen, Bis-(triphenylphosin der VIII. Gruppe einnimmt, wie aus verschiedensten 5° phin) - nickel - (0) - stilben, Bis - triphenylphosphin)-Veröffentlichungen, unter anderem aus dem Max- nickel-(O)-tolan, Bis-OricyclohexylphosphinJ-nickel-Planck-Institut für Kohlenforschung in Mülheim/Ruhr, (0) - äthylen, Bis - (tripiperidinophosphin) - nickel - (O)-bekannt ist. So kann man beispielsweise gewisse äthylen und Bis-(triphenylphosphin)-nickel-(0)-buta-Oligomerisationsreaktionen, insbesondere cyclische dien genannt.low atomic number seldom, if not not at all, with various electron donors, cyclo is possible or common. In addition, it is known that octadiene-nickel- (0) -bis- (triphenylphosphine) s bis-triphe, for example, nickel occupies a very special position from various 5 ° phin) - nickel - (0) - stilbene, bis - triphenylphosphine) publications, including from Max-nickel- (O) -tolane, bis-oricyclohexylphosphineJ-nickel-Planck-Institut für Kohlenforschung in Mülheim / Ruhr, (0) - ethylene, bis - (tripiperidinophosphine) - nickel - (O) - is known. For example, certain ethylene and bis (triphenylphosphine) nickel (0) bututa oligomerization reactions, especially cyclic diene, can be called.
Oligomerisationsreaktionen, nur mit Nickel durch- 55 Das erfindungsgemäße Verfahren kann mit und führen. Ähnliches gilt für katalytische Verfahren. ohne Lösungsmittel, vorzugsweise aber in GegenwartOligomerization reactions, only carried out with nickel. The process according to the invention can be carried out with and to lead. The same applies to catalytic processes. without solvent, but preferably in the presence
Die Erfindung betrifft ein Verfahren zur Her- eines Lösungsmittels ausgeführt werden. Als Lösteilung von neuen Komplexen von nullwertigem sungsmittel kommen solche in Frage, die weder die Nickel, die als einzige Liganden Sauerstoff und einzusetzenden Übergangsmetallkomplexe angreifen. Elektronendonatoren enthalten, das dadurch gekenn- 60 noch selbst durch den aktivierten Sauerstoff angezeichnet ist, daß man Komplexe aus nullwertigem griffen werden. Geeignete Lösungsmittel sind beiNickel und Elektronendonatoren, die a) Heteroatome spielsweise: Aliphatische, cycloaliphatische und aromit freien Elektronenpaaren und/oder b) Mehrfach- matische Kohlenwasserstoffe, Äther und Ester wie bindungen mit π-Elektronensystemen enthalten, mit z. B. Hexan, Cyclohexan, Benzol, Gemische gesättigter molekularem Sauerstoff bei Temperaturen von —100 65 Kohlenwasserstoffe Sdp. 60 bis 200°C), Tetrahydrobis +75°C umsetzt. furan, Dioxan, Diäthyläther. Auch Gemische dieserThe invention relates to a method for producing a solvent. As a division of the solution of new complexes of zero-valent solvent, those that are neither the Nickel, the only ligands that attack oxygen and the transition metal complexes to be used. Contain electron donors, which are thereby marked by the activated oxygen is that complexes can be grasped from zero-valued. Suitable solvents are for nickel and electron donors, the a) heteroatoms, for example: aliphatic, cycloaliphatic and aromite free electron pairs and / or b) polyhydric hydrocarbons, ethers and esters such as contain bonds with π-electron systems, with z. B. hexane, cyclohexane, benzene, mixtures of saturated molecular oxygen at temperatures of -100 65 hydrocarbons bp 60 to 200 ° C), Tetrahydrobis + 75 ° C. furan, dioxane, diethyl ether. Even mixtures of these
Erfindungsgemäß reagiert z. B. Tetrakis-(triphenyl- Lösungsmittel sind verwendbar. Das erfindungsgemäße phosphin)-nickel-(0) in Suspension bereits bei —80°C Verfahren wird bei Temperaturen von —100 bisAccording to the invention, for. B. Tetrakis (triphenyl solvents can be used phosphine) -nickel- (0) in suspension already at -80 ° C process is carried out at temperatures from -100 to
3 43 4
+750C, insbesondere von —80 bis +500C durch- R ·. ·., , gefuhrt.+75 0 C, in particular from -80 to +50 0 C through R ·. ·., , guided.
Die neuen Sauerstoffliganden enthaltenden Korn- Zur Darstellung des Bis-(triphenylphosphin)-nickel-The new grain containing oxygen ligands- To represent the bis- (triphenylphosphine) -nickel-
plexe des Nickels mit Elektronendonatoren können (0) · O2 kann man auch von Bis-(triphenylphosphin)-plexes of nickel with electron donors can (0) O 2 can also be obtained from bis (triphenylphosphine) -
zur Übertragung von Sauerstoff verwendet werden. 5 nickel-(0)-tolan ausgehen. 15,56 g dieses Komplexesused to transfer oxygen. 5 run out of nickel (0) tolan. 15.56 g of this complex
Beispielsweise gehen die genannten Komplexe bei werden in 100 g Äther suspendiert, bei —78° C mitFor example, the complexes mentioned are suspended in 100 g of ether at -78 ° C
Zersetzung in Sauerstoffverbindungen der am Metall Sauerstoff behandelt (Aufnahme 0,64 g). Man reinigtDecomposition in oxygen compounds treated with oxygen on the metal (uptake 0.64 g). One cleans
gebundenen Donatoren über. In gleicher Weise kann gemäß Beispiel 1, die Ausbeute ist praktisch quan-bound donors over. In the same way, according to Example 1, the yield is practically quant
ein Überschuß an Elektronendonator katalytisch am titativ.an excess of electron donor catalytically am titative.
Metall oxydiert werden. io B e i s ρ i e 1 4Metal can be oxidized. io B e i s ρ i e 1 4
B e i s ρ i e 1 1 Das Bis-(triphenylphosphin)-nickel-(0) - Oa wird so-B eis ρ ie 1 1 The bis- (triphenylphosphine) -nickel- (0) - O a is thus-
35 g Tetrakis-(triphenylphosphin)-nickel in 350 g fort rein erhalten, wenn man die Suspension von35 g of tetrakis (triphenylphosphine) nickel in 350 g of pure obtained when you use the suspension of
Äther nehmen bei —78°C Ig Sauerstoff auf. Dabei 22,6 g Bis-(triphenylphosphin)-nickel-(0)-äthyien inEthers take up oxygen at -78 ° C. Thereby 22.6 g of bis (triphenylphosphine) nickel (0) ethyien in
entsteht aus dem rotbraunen Tetrakis-(triphenylphos- 15 150 g Äther bei —78°C mit 1,14 g Sauerstoff umsetzt.
phin)-nickel der gelbe Bis-(triphenylphosphin)-nickel-(0)-sauerstoffkomplex,
der durch Extraktion bei
—78°C mit kaltem Äther vom mitentstandenen Triphenylphosphin
befreit wird. Läßt man danach diethe red-brown tetrakis (triphenylphosphine) converts 150 g of ether at -78 ° C with 1.14 g of oxygen
-78 ° C is freed from the resulting triphenylphosphine with cold ether. If you then leave the
reine Verbindung — in Äther suspendiert — auf eine 20 21,6 g Bis-(tricyclohexylphosphin)-nickel-(0)-äthylen Temperatur über —35°C kommen, so tritt unter in 250 g Äther suspendiert nehmen bei —78=C 1,10 g Braunfärbung Zersetzung ein. Aus dem erhaltenen Sauerstoff auf. Man erhält 21 g Bis-(tricyclohexyl-Gemisch läßt sich das elementare Nickel mit ver- phosphin)-nickel-(0) · O2 in reiner Form. Gefunden dünnter Salzsäure entfernen. Die Ätherlösung hinter- Ni 8,89 %, berechnet Ni 9,01 °/0. läßt beim Eindampfen 17 g Triphenylphosphinoxyd, 25 . . d. h., das am Sauerstoffkomplex gebundene Tri- Beispiel ö phenylphosphin ist praktisch zu 100 °/0 oxydiert Reines Bis-(tripiperidinophosphin)-nickel-(0) - O2 erworden. Der gelb gefärbte, bei —78°C mit kaltem hält man, wenn man in die Suspension von 3,01 g Bis-Äther von mitentstandenem Triphenylphosphin be- (tripiperidinophosphin)-nickel-(0)-äthylenin35 g Äther freite Komplex hatte einen Nickelgehalt von 9,54°/0 30 bei —78°C Sauerstoff einleitet. In etwa 1,5 Stunden (berechnet für Bis-(PPh3)-Ni-(O2) 9,54% Ni,). werden 0,15 g O2 aufgenommen. Man erhält 3,0 gpure compound - suspended in ether - come to a temperature of 20-21.6 g of bis (tricyclohexylphosphine) nickel (0) ethylene temperature above -35 ° C, then take it suspended in 250 g of ether at -78 = C 1 , 10 g brown color decomposition a. From the oxygen obtained. 21 g of bis (tricyclohexyl mixture) are obtained, the elemental nickel can be quenched in pure form with phosphine) -nickel (0) · O 2. Remove found dilute hydrochloric acid. The ether solution rear Ni 8.89%, calculated Ni 9.01 ° / 0th leaves on evaporation 17 g of triphenylphosphine oxide, 25. . that is, the bound oxygen complex at tri- phenylphosphine ö example is practically 100 ° / 0 Pure oxidized bis (tripiperidinophosphin) -nickel- (0) - you purchased it O 2. The yellow colored, cold at -78 ° C is kept if you add a nickel content to the suspension of 3.01 g of bis-ether of the triphenylphosphine (tripiperidinophosphine) -nickel- (0) -äthylenin 35 g of ether-free complex of 9.54 ° / 0 30 introduces oxygen at -78 ° C. In about 1.5 hours (calculated for Bis- (PPh 3 ) -Ni- (O 2 ) 9.54% Ni,). 0.15 g of O 2 are absorbed. 3.0 g are obtained
Komplex. Gefunden Ni 8,75%, berechnet Ni 8,92%.Complex. Found Ni 8.75%, calculated Ni 8.92%.
40,8 g Bis-(triphenylphosphin)-nickel(-0)-stilben in B e i s ρ i e 1 740.8 g bis (triphenylphosphine) nickel (-0) stilbene in B e i s ρ i e 1 7
200 g Äther suspendiert nehmen bei —78°C 1,68 g 35 3,06 g Bis-(triphenylphosphin)-nickel-(0)-zimtalde-200 g of ether, suspended, take 1.68 g 35 3.06 g of bis (triphenylphosphine) nickel (0) cinnamon alde- at -78 ° C.
Sauerstoff auf. Das entstandene Bis-(triphenylphos- hyd, suspendiert in 35 g Äther, nehmen bei —78°COxygen on. The resulting bis (triphenylphosphide), suspended in 35 g of ether, take at -78 ° C
phin)-nickel-(0) · O2 wird gemäß Beispiel 1 gereinigt. 0,14 g Sauerstoff auf. Nach dem Filtrieren undPhin) -nickel- (0) · O 2 is purified according to Example 1. 0.14 g of oxygen. After filtering and
Ausbeute praktisch quantitativ, Nickelgehalt 9,75% Waschen mit Äther bei —78"C verbleibt der reineYield practically quantitative, nickel content 9.75%. Washing with ether at -78 "C remains pure
(ber. Ni 9.54%)· Bis-(triphenylphosphin)-nickel-(0)-sauerstoffkomplex.(calculated Ni 9.54%) bis (triphenylphosphine) nickel (0) oxygen complex.
/o>/ o>
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEST026261 | 1966-12-17 | ||
| DEST026261 | 1966-12-17 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1593565A1 DE1593565A1 (en) | 1970-07-23 |
| DE1593565B2 DE1593565B2 (en) | 1973-01-18 |
| DE1593565C true DE1593565C (en) | 1973-08-23 |
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