DE2148925C3 - Process for the preparation of transition metal complexes - Google Patents
Process for the preparation of transition metal complexesInfo
- Publication number
- DE2148925C3 DE2148925C3 DE2148925A DE2148925A DE2148925C3 DE 2148925 C3 DE2148925 C3 DE 2148925C3 DE 2148925 A DE2148925 A DE 2148925A DE 2148925 A DE2148925 A DE 2148925A DE 2148925 C3 DE2148925 C3 DE 2148925C3
- Authority
- DE
- Germany
- Prior art keywords
- transition metal
- metal complexes
- preparation
- mmol
- benzene
- 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
- 238000000034 method Methods 0.000 title description 4
- 229910052723 transition metal Inorganic materials 0.000 title description 3
- 150000003624 transition metals Chemical class 0.000 title description 3
- 238000002360 preparation method Methods 0.000 title description 2
- 230000007704 transition Effects 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- -1 alkyl radical Chemical group 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052698 phosphorus Chemical group 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000005840 aryl radicals Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- 239000011574 phosphorus Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- MLBZLJCMHFCTQM-UHFFFAOYSA-N (2-methylphenyl)-diphenylphosphane Chemical compound CC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MLBZLJCMHFCTQM-UHFFFAOYSA-N 0.000 description 1
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000006145 Eagle's minimal essential medium Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BZFFGVWWHZFAFP-UHFFFAOYSA-N [2-(2-methylphenyl)phenyl]phosphane Chemical compound CC1=CC=CC=C1C1=CC=CC=C1P BZFFGVWWHZFAFP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001975 deuterium Chemical group 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/38—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes
- C07C2/40—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes of conjugated dienes
- C07C2/403—Catalytic processes
- C07C2/406—Catalytic processes with hydrides or organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
- C07C2/44—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion of conjugated dienes only
- C07C2/46—Catalytic processes
- C07C2/465—Catalytic processes with hydrides or organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3882—Arylalkanephosphonic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
- C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
,NiCl2,, NiCl 2 ,
worin X Stickstoff oder Phosphor, R einen Alkylrest oder einen Arylrest, M Ni, Pt oder Pd und λ und /ι, voneinander verschieden 0 oder 1 bedeuten, dadurch gekennzeichnet, daß man den entsprechenden Alkalikomplex mit einem komplexen Nickel-, Platin- oder Palladiumhalogenid in Gegenwart eines inerten Lösungsmittels bei -70 bis +500C umsetzt.wherein X is nitrogen or phosphorus, R is an alkyl radical or an aryl radical, M Ni, Pt or Pd and λ and / ι, different from each other 0 or 1, characterized in that the corresponding alkali complex with a complex nickel, platinum or palladium halide in the presence of an inert solvent at -70 to +50 0 C implemented.
X' X' LX 'X' L
^vmlm, won» M, L und X' die oben angegeben»« Bedeutungen besitzen. . ^ vmlm, where "M, L and X 'have the""meanings given above. .
SteStion wird in einem merten Losungsmrt el. ,o wie einem Kohlenwasserstoff, emem Äther .nk-r Sfem Amin durchgeführt. Die Temperatur be.ragt vorzugsweise zwischen 0 und JU cSteStion is in a merten Losungsmrt el., O as a hydrocarbon, ether EMEM .nk-r SFEM amine performed. The temperature is preferably between 0 and JU c
S^ erfindungsgemäß herstellbaren übergangsmetalSompTexe sfellen eine neue Klasse von metall· „ organSen Verbindungen dar. <üe einkermg s.nd und im Gegensatz zu den bekannten zwe.kern.gen una .,™_„ JLw.„ Derivaten von übergangsmeiallen • ι _...i.,·:. ^K. Aktivität fiir ver- S ^ inventively produced übergangsmetalSompTexe sfellen "represents organSen connections. <Üe einkermg s.nd and in contrast to the known zwe.kern.gen una., ™ _" a new class of metal · JLW. "Derivatives of übergangsmeiallen • ι _. ..i., · :. ^ K. Activity for
Die Erfindung betrifft ein Verfahren zur Herstellung von übergangsmetallkomplexen der FormelThe invention relates to a process for the preparation of transition metal complexes of the formula
in undin and
worin X Stickstoff oder Phosphor, R einen Alkylrest oder einen Arylrest. M Ni, Pt oder Pd und η und n, voneinander verschieden 0 oder 1 bedeuten, das dadurch gekennzeichnet ist, daß man den entsprechenden Alkalikomplex mit einem komplexen Nickel-, Platin- oder Palladiumhalogenid in Gegenwart eines inerten Lösungsmittels bei -70 bis +50' C umsetzt. Das erfindungsgeaiälße Verfahren verläuft nach dem folgenden Reaktiomsschema:wherein X is nitrogen or phosphorus, R is an alkyl radical or an aryl radical. M Ni, Pt or Pd and η and n, are different from one another 0 or 1, which is characterized in that one of the corresponding Alkali complex with a complex nickel, platinum or palladium halide in the presence of a inert solvent at -70 to +50 'C converts. The method according to the invention proceeds according to the following reaction scheme:
+ L2MXl+ L 2 MXl
+ 2M1X1+2L+ 2M 1 X 1 + 2L
worin M1 ein Alkalimetall, wie Lithium» Natrium oder Kalium, darstellt und M und X die vorstehenden Bedeutungen besitzen. Beispiele für verwendbare Verbindungen sind l-Lithium-2-methyl-N,N-dimethylaminobenzoi und l-Methylkälium-2-diphenylphosphiiibenzol. L2MX'2 stellt eine Koordinationsverbindung dar, worin X1 ein Halogenid, wie Cl", Br" öder J" und L einen organischen Liganden des Typs YR'2, worin Y O öder S bedeutet, oder des Typs ZR'3, worin Z N oder P darstellt und R1 einen phin.where M 1 is an alkali metal, such as lithium, sodium or potassium, and M and X have the meanings given above. Examples of compounds which can be used are 1-lithium-2-methyl-N, N-dimethylaminobenzoi and 1-methylkälium-2-diphenylphosphine benzene. L 2 MX ' 2 represents a coordination compound in which X 1 is a halide such as Cl ", Br" or J "and L is an organic ligand of the type YR' 2 , in which YO is or S, or of the type ZR ' 3 , in which Z represents N or P and R 1 represents a phin.
Die überraschende katalytische Aktivität der erfindungsgemäß herstellbaren Übergangsmetallkomplexe wird durch die Oligomeri««nion von Olefinen, Dienen und Acetylenverbindungen, durch die Kohlenmonoxyd-Einfügung mit anschließender Formylierung des organischen Rests, durch die Reaktion mit Wasserstoff, wobei man sehr wirksame Hydrierkatalysatoren erhält, verdeutlicht. Hier bedeuten: Me ~ CH1, At = C2H5.The surprising catalytic activity of the transition metal complexes which can be prepared according to the invention is illustrated by the oligomeric ion of olefins, dienes and acetylene compounds, by the addition of carbon monoxide with subsequent formylation of the organic radical, by the reaction with hydrogen, which gives very effective hydrogenation catalysts. Here mean: Me ~ CH 1 , At = C 2 H 5 .
Die folgenden Beispiele dienen zur Erläuterung der Erfindung.
Beispiel!The following examples serve to illustrate the invention.
Example!
Eine Mischung aus 22 mMol o-Tolylphenylphosphin und 22 mMol Kaltum-tert.-butylat in η Hexan wurde mit einer Lösung von 22 mMol Butyllithium in η-Hexan bei 25C C unter einer inerten Atmosphäre umgesetzt. Man erhielt sofort eine roten Niederschlag, der aus l-Methylkalium-2-diphenylphosphitibenzol [K(bP)j bestand und nur geringe Mengen Kaliumtert.-butylat enthielt, von dem dieser Niederschlag durch Extraktion mit Benzol gereinigt werden konnte. Das Produkt ergab bei der Behandlung mit D2O o-Tolyldiphenylphosphin mit einem Deuteriumatom in der Benzylsteüung und einem Verhältnis zwischen dem NMR-Signal des aromatischen Protons (τ = 7,25) zu dem NMR-Signal der Benzylprotonen (t = 2,38) von 7.A mixture of 22 mmol of o-Tolylphenylphosphin and 22 mmol Kaltum tert-butoxide in hexane η was reacted with a solution of 22 mmol of butyllithium in hexane at 25 C η-C under an inert atmosphere. A red precipitate was immediately obtained which consisted of 1-methylpotassium-2-diphenylphosphitibenzene [K (bP) j and contained only small amounts of potassium tert-butoxide, from which this precipitate could be purified by extraction with benzene. On treatment with D 2 O, the product gave o-tolyldiphenylphosphine with a deuterium atom in the benzyl position and a ratio between the NMR signal of the aromatic proton (τ = 7.25) to the NMR signal of the benzyl protons (t = 2.38 ) from 7.
Dann wurde eine Lösung von 2,15 g (5,89 mMol) (PAt3J2NiCl2 in 10 ml Benzol langsam zu einer Suspension von [K(bP)] (4,07 g, 11,8 mMol) in 30 ml Benzol unter Rühren und unter inerter Atmosphäre zugegeben. Nach der Zugabe wurde der rote Niederschlag abfiltriert und die erhaltene Lösung zur Trockne eingedampft, worauf man die HauptmengeThen a solution of 2.15 g (5.89 mmol) of (PAt 3 J 2 NiCl 2 in 10 ml of benzene was slowly added to a suspension of [K (bP)] (4.07 g, 11.8 mmol) in 30 ml of benzene was added with stirring and under an inert atmosphere After the addition, the red precipitate was filtered off and the resulting solution was evaporated to dryness, whereupon the main amount
von Triäthylphosphin durch Erhitzen bei einem Vakuum von 0,1 Torr, auf SO' C entfernte.of triethylphosphine by heating at a vacuum of 0.1 torr to SO 'C removed.
Die letzten Triätbylphosphinspuren wurden durch Waschen mit α-Hexan beseitigtThe last traces of trietbylphosphine were through Washing with α-hexane eliminated
Pie verbleibende dunkelgelbe Masse wurde aus Tetrahydrofuran umkristallisiert und ergab gelbe nadeiförmige Kristalle mit den folgenden Analysenwerten: Pie remaining dark yellow mass turned out Tetrahydrofuran recrystallized and gave yellow needle-shaped crystals with the following analysis values:
Berechnet ... C74,91, H 5,25%;
gefunden ... C 75,58, H 5,52%.Calculated ... C74.91, H 5.25%;
found ... C 75.58, H 5.52%.
Die Verbindung ist an der Luft und in dem festen Zustand nicht stabil und reagiert mit Kohlenmonoxyd unter Bildung eines Nickelderivates mit charakteristischen IR-Banden bei 2075, 1990 — 1950 cm1.The compound is not stable in air and in the solid state and reacts with carbon monoxide to form a nickel derivative with characteristic IR bands at 2075, 1990 - 1950 cm 1 .
Durch Umsetzung mit Wasserstoff bildete sich eine Hydridverbindung, die eine IR-Bande bei 1695 cm"1 zeigte. 0,5 mMol der Nickelverbindung wurden in einen 250-ccm-Wiegeautoklav eingebracht, der zuvor durch wiederholtes Evakuieren und Füllen mit Stickstoff von Luft befreit worden war.Reaction with hydrogen formed a hydride compound which showed an IR band at 1695 cm " 1. 0.5 mmol of the nickel compound was introduced into a 250 cc weighing autoclave which had previously been freed from air by repeated evacuation and filling with nitrogen was.
Dann wurden bei Raumtemperatur 80 g wasserfreies Butadien zugegeben, worauf der Autoklav auf 100 C erhitzt wurde, worauf man während 8 Stunden rührte. Nach Ablauf der Untersuchung wurde die Reaktion mit 20 ecm mit Chlorwasserstoffsäure angesäuertem Methanol gestoppt. Der Autoklav wurde dann geöffnet und der Inhalt destilliert, um das Lösungsmittel, das Methanol und das nichtumgesetzte Butadien abzutrennen. Der Rest wurde einer fraktionierten Vakuumdestillation unterzogen. Man erhielt zwei Fraktionen und einen Rückstand, was einer Butadien-Umwandlung von 30% entspricht.80 g of anhydrous butadiene were then added at room temperature, whereupon the autoclave opened 100 C was heated, whereupon the mixture was stirred for 8 hours. At the end of the investigation, the Reaction with 20 ecm acidified with hydrochloric acid Methanol stopped. The autoclave was then opened and the contents distilled to obtain the Separate solvent, the methanol and the unreacted butadiene. The rest became one subjected to fractional vacuum distillation. Two fractions and a residue were obtained corresponds to a butadiene conversion of 30%.
Die erste Fraktion {etwa 10% der Gesamtmenge) bestand hauptsächlich, wie sich durch gaschromatographische Analyse zeigte, aus Cyclooctadien. Die zweite Fraktion (etwa 50% der Gesamtmenge) bestand, wie sich durch gaschromatographische Analyse zeigte, aus Cyclododecatrien. Der Rest (etwa 40%) bestand aus nichtdestillierten Butadienoligomeren.The first fraction (about 10% of the total) consisted mainly as indicated by gas chromatography Analysis showed from cyclooctadiene. The second fraction (about 50% of the total) consisted of as shown by gas chromatographic analysis, from cyclododecatriene. The rest (about 40%) consisted of undistilled butadiene oligomers.
20 ml einer Benzollösung von 2,45 mMol cis-(PBu3I2PtCl2 wurden zu einer Suspension von 1.55 g (4,9 mMol) [K(bP)] in 20 ml Benzol unter Rühren und unter inerter Atmosphäre zugegeben. Der sich bildende weiße Niederschlag wurde abfiltriert, mi ι Wasser und schließlich mit Methylalkohol gewaschen. Durch Kristallisation aus siedendem Tetrahydrofuran erhielt man Pt(bP)2 in einer Ausbeute von etwa 30% in Form von weißen Nadeln, die folgende Analysenwerte aufwiesen:20 ml of a benzene solution of 2.45 mmol of cis- (PBu 3 I 2 PtCl 2 were added to a suspension of 1.55 g (4.9 mmol) [K (bP)] in 20 ml of benzene with stirring and under an inert atmosphere The white precipitate that formed was filtered off, washed with water and finally with methyl alcohol. Crystallization from boiling tetrahydrofuran gave Pt (bP) 2 in a yield of about 30% in the form of white needles which had the following analytical values:
Berechnet ..
gefunden ..Calculated ..
found ..
C 61,2, H 4,29%.
C 61,1, H 4,29%.C 61.2, H 4.29%.
C 61.1, H 4.29%.
Die analoge Palladium-Verbindung erhielt man in ähnlicher Weise, ausgehend von trans-( PAt,),PdCI2 in Form eines weißen kristallinen Produktes der Formel Pd(bP)2 mit folgenden Analysenwerten:The analogous palladium compound was obtained in a similar manner, starting from trans- (PAt,), PdCl 2 in the form of a white crystalline product of the formula Pd (bP) 2 with the following analytical values:
Berechnet
gefundenCalculated
found
C 69,4, H 4,25%;
C 69,18, H 4,8%.C 69.4, H 4.25%;
C 69.18, H 4.8%.
20 ml einer Benüolsuspension Von l-Lilhium-2-methyl-N,N-dimethylaminobenzol
[Li(bN)] (2,8 g, 20 mMol) wurden mit 20 ml einer Benzollösung von 4,46 g (10 mMol) trans-(SÄt2)2PtCi2 unter Rühren
und unter inerter Atmosphäre umgesetzt. Die so erhaltene weiße Suspension wurde durch Filtrieren
abgetrennt.
5 20 ml of a benzene suspension of l-Lilhium-2-methyl-N, N-dimethylaminobenzene [Li (bN)] (2.8 g, 20 mmol) were mixed with 20 ml of a benzene solution of 4.46 g (10 mmol) trans- reacted (sows 2) 2 PtCl 2 with stirring and under an inert atmosphere. The white suspension thus obtained was separated by filtration.
5
α) Die weiße feste Verbindung wurde mit Wasser und Methylalkohol gewaschen und in siedendem Aceton kristallisiert, so daß man ein weißes kristallines Produkt erhieät, das in einer im ίο Vakuum abgeschmolzenen Kapillare sich bei 248 C zu zersetzen begann und wahrscheinlich aus dem cis-Isomeren von Pt(bN), bestand, das folgende Analysenwerte aufwies:α) The white solid compound was with water and methyl alcohol and crystallized in boiling acetone to give a white crystalline product, which is contained in a capillary that is melted in a vacuum 248 C began to decompose and probably consisted of the cis isomer of Pt (bN), the showed the following analysis values:
C 46,60, H 5,18, N 6,04%;
C 47.08, H 5,32, NC 46.60, H 5.18, N 6.04%;
C 47.08, H 5.32, N
Berechnet
gefundenCalculated
found
b) Die filtrierte Lösung wurde zur Trockne eingedampft, und der Rückstand wurde aus Aceton erneut umkristallisiert, so daß man ein ungefärbtes kristallines Produkt mit einem in einer im Vakuum abgeschmolzenen Kapillare gemessener. Zersetzungspunkt von 198 C erhielt, was wahrscheinlich das trans-Isomere von PKbN)2 ist.b) The filtered solution was evaporated to dryness and the residue was recrystallized again from acetone, so that an uncolored crystalline product was measured with a capillary sealed in vacuo. Decomposition point of 198 C obtained, which is probably the trans isomer of PKbN) 2 .
Es wurden folgende Analysen werte gefunden:
C 46,6. H 5,10, N 6,05%.The following analysis values were found:
C 46.6. H 5.10, N 6.05%.
Dieses Isomere war sehr reaktiv usid reagierte z. B.This isomer was very reactive and reacted e.g. B.
schnell mit CO unter Bildung eines Acylderivates,quickly with CO to form an acyl derivative,
das eine IR-Absorptionsbande bei 1606 cm ' zeigte, wobei die Formel wie fDlgt dargestellt werden kann:which showed an IR absorption band at 1606 cm ', where the formula can be represented as f Dlgt:
Pt(O = C -bN)2.Pt (O = C -bN) 2 .
Analyse
Berechnet
gefundenanalysis
Calculated
found
C 46,7, H4.6Z N :>,39%;
C 46,6. H 4,84. N :5,63%.C 46.7, H4.6Z N:>, 39%;
C 46.6. H 4.84. N: 5.63%.
Eine Tetrahydrofuran-Lösung der Verbindung reagierte bei 25 C und bei einer Atmosphäre mit H2 unter Bildung von metallischem Pt.A tetrahydrofuran solution of the compound reacted with H 2 at 25 C and in an atmosphere to form metallic Pt.
Unter Anwendung des im Beispiel 3 beschriebenen Verfahrens, jedoch ausgehend von (SÄt2)2PdCl2 und (PÄtj)2NiCI2, erhielt man aus der Benzollösung PdIbN)2 und Ni(bN)2.Using the method described in Example 3, but starting from (SÄt 2 ) 2 PdCl 2 and (PÄtj) 2 NiCl 2 , PdIbN) 2 and Ni (bN) 2 were obtained from the benzene solution.
Ni(bN), stellt eine seh· reaktive, gelbe, kristalline Verbindung dar, die. wenn sie in Lösung gehalten wird, sich bei Raumtemperatur zersetzt.Ni (bN) represents a visually reactive, yellow, crystalline Connection represents that. if kept in solution, decomposes at room temperature.
PdIbN)2 ist ein weißer Feststoff, der sich in Lösung langsam unter Bildung von metallischem Pd zersetzt.PdIbN) 2 is a white solid that slowly decomposes in solution to form metallic Pd.
Analyse:
Berechnet
gefundenAnalysis:
Calculated
found
C 57.69, H 6.41, N 7,47%;
C 58.02. H 6.7, N 7.48%.C 57.69, H 6.41, N 7.47%;
C 58.02. H 6.7, N 7.48%.
In Anwesenheit von einem Olefin und Wasserstoff beobachtet man eine schnelle Hydrierung zu einem Paraffin.Rapid hydrogenation to one is observed in the presence of an olefin and hydrogen Paraffin.
Zum Beispiel wurden 20 ml Cyclohexen bei Atmosphärendruck und Raumtemperatur in GegenwartFor example, 20 ml of cyclohexene were present at atmospheric pressure and room temperature
(>o von 0,12 Mol der Palladiumverbindung in 30 Stunden hydriert, Die Umwandlung zu Cyclohexan betrug,(> o of 0.12 mol of the palladium compound hydrogenated in 30 hours, the conversion to cyclohexane was
wie sich gaschromatographisch zeigen ließ, 32%.as could be shown by gas chromatography, 32%.
Die Verbindungen M(bN)2(M = Ni, Pd, Pt) zeigtenThe compounds M (bN) 2 (M = Ni, Pd, Pt) showed
charakteristische IR-Banden bei etwa 1570 bis 1500characteristic IR bands around 1570 to 1500
(15 cm~' und 850 cm"1, die in dem IR-Spektrum des freien Amins oder dessen Komplexen nicht oder nur schwach vorhanden sind. (15 cm -1 and 850 cm "1, which are not or only weakly present in the IR spectrum of the free amine or its complexes.
Claims (1)
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DE2148925B2 DE2148925B2 (en) | 1973-10-25 |
DE2148925C3 true DE2148925C3 (en) | 1975-09-04 |
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BE (1) | BE773164A (en) |
CH (1) | CH553822A (en) |
DE (1) | DE2148925C3 (en) |
FR (1) | FR2108686A5 (en) |
GB (1) | GB1336779A (en) |
LU (1) | LU63978A1 (en) |
NL (1) | NL7113380A (en) |
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-
1971
- 1971-09-28 BE BE773164A patent/BE773164A/en unknown
- 1971-09-29 GB GB4545171A patent/GB1336779A/en not_active Expired
- 1971-09-29 FR FR7135026A patent/FR2108686A5/fr not_active Expired
- 1971-09-29 LU LU63978D patent/LU63978A1/xx unknown
- 1971-09-29 NL NL7113380A patent/NL7113380A/xx not_active Application Discontinuation
- 1971-09-30 CH CH1419871A patent/CH553822A/en not_active IP Right Cessation
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NL7113380A (en) | 1972-04-05 |
CH553822A (en) | 1974-09-13 |
FR2108686A5 (en) | 1972-05-19 |
DE2148925A1 (en) | 1972-04-06 |
LU63978A1 (en) | 1972-03-01 |
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