GB2058074A - Palladium complexes - Google Patents

Palladium complexes Download PDF

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GB2058074A
GB2058074A GB7929389A GB7929389A GB2058074A GB 2058074 A GB2058074 A GB 2058074A GB 7929389 A GB7929389 A GB 7929389A GB 7929389 A GB7929389 A GB 7929389A GB 2058074 A GB2058074 A GB 2058074A
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reaction
palladium complex
palladium
complex
hydrogenation
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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
    • 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
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • 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
    • 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
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • 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 System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • 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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

A novel palladium complex having a molecular structure: <IMAGE> where L1 and L2 are weakly co- ordinated solvento-ligands (e.g. acetone, acetonitrile, methanol, ethanol etc) and where L3-Y-L4 is a bidentate ligand containing groups L3 and L4 each of which has a Group V or Group VI donor atom attached to the palladium atom, L3-Y-L4 being of the form either R1R2E1-Y-E2R3R4 or R1E3-Y-E4R2, where each of R1, R2, R3 and R4 is an alkyl or aryl group, where Y is either (CH2)n in which n is 1, 2 or 3, or o-phenylene, or cis-vinyl, and where each of E1 and E2 is selected from nitrogen, phosphorus, arsenic, antimony and each of E3 and E4 is selected from oxygen, sulphur or selenium, X<-> is a "non-coordinating" anion such as perchlorate. The complex is useful as a catalyst, e.g. in the hydrogenation of alkenes or in alcoholysis reactions (for silanes).

Description

SPECIFICATION Palladium complexes suitable for use as catalysts The present invention relates to palladium complexes suitable for use as catalysts in organic reactions.
Avariety of palladium (II) complexes are well known as catalysts for many organic reactions. However, for certain commercially important reactions such as the hydrogenation of alkenes palladium (II) complexes show little activity. Rhodium (I) complexes are usually employed in such reactions instead but are generally more costly since rhodium metal is significantly more expensive than palladium.
The purpose of the present invention is to provide a novel catalyst, generally less expensive than rhodium complexes, suitable for use in one or more organic reactions particularly where known palladium complexes are unsuitable.
According to the present invention in a first aspect there is provided a palladium complex having a molecular structure:
where L1 and L2 are weakly co-ordinated solvento-ligands and where L3-Y-L4 is a bidentate ligand containing groups L3 and 4 each of which has a Group V or Group VI donor atom attached to the palladium atom, L3-Y-L4 being of the form either R1R2E1-Y-E2R3R4 or R1E3-Y-E4R2, where each of R1R2,R3 and R4 is an alkyl or aryl group (which may or may not contain substituent groups), where Y is either (CH2)n in which n is 1,2 or 3, or o-phenylene, or cis-vinyl, and where each of E1 and E2 is selected from nitrogen, phosphorus, arsenic, antimony and each of E3 and E4 is selected from oxygen, sulphur or selenium, X- is a non-coordinating anion.
By a "non-coordinating" anion is meant one which does not interact with the palladium atom. X- may be Cl04-, BF4- or PFG-.
Preferably, L3 is the same as L4 although it need not be. Thus R1, R2, R3 and R4 may be the same or different groups and E1 may or may not be the same as E2.
Preferably, E1 and E2 are both phosphorus.
Preferably, R1, R2, R3 and R4 are all phenyl groups.
Preferably, Y is CH2CH2.
Solvento-ligands are those which commonly form solvents. Those skilled in the art and science of co-ordination chemistry will appreciate that weakly co-ordinated solvento-ligands include acetone, acetonitrile, benzonitrile, o-toluonitrile, methanol, ethanol, tetrahydrofuran, water and related ligands.
According to the present invention in a second aspect there is provided a method of carrying out an organic reaction in the presence of a catalyst, characterised in that the catalyst is a palladium complex as defined in the first aspect above.
The reaction in the second aspect may be the hydrogenation of an unsaturated organic compound, eg an alkene, orthe alcoholysis of a silane.
Thus, in the case of hydrogenation of alkenes palladium complexes embodying the invention may be used as catalysts instead of rhodium complexes, known palladium complexes being largely unsuitable.
In the case of hydrogenation reactions, the complex used may be a complex according to the first aspect above in which L1 and L2 (see Formula I above) are acetone and L3-Y-L4 is 1,2-bis(diphenylphosphino)ethane.
In the case of alcoholysis reactions the complex used may be a complex according to the first aspect above in which L1 and L2 (Formula I) are methyl alcohol or ethyl alcohol and L3-Y-L4 is 1,2bis(diphenylphosphino)ethane.
The palladium complex used in the second aspect of the invention may be prepared separately before introduction into the vessel or apparatus used to carry out the organic reaction. Alternatively, the palladium complex may be prepared in situ in the reaction vessel or apparatus prior to the reaction being established.
Embodiments of the present invention will now be described by way of example.
Example 1 Various palladium complexes oftheform shown in Formula I above having L3-Y-L4 = 1,2 bis(diphenylphosphinolethane were isolated by the following method.
The complex dichloro[1 ,2-bis(diphenylphosphino)ethane]palladium(ll) and two molar equivalents of the salt silver (I) perchlorate were extensively dried in vacuo and added together in a suitable dried solvent system. The solvent system consisted of the non-donor solvents dichloromethane and benzene and the donor solvent (where the donor solvent could be acetone, acetonitrile, benzonitrile, o-toluonitrile, methanol, ethanol, tetrahydrofuran or related solvents). After two hours stirring a white precipitate was formed which was filtered off to leave a clear yellow solution. The complexes could be isolated by reducing the volume of the solution in vacuo until precpitation begins and then completing precipitation by the addition of dried diethylether.The complexes [Pd(Ph2PCH2CH2PPh2) (donor solvent)2][CIO4J2 could be isolated as such for the donor solvents acetone, acetonitrile and benzonitrile. For the donor solvents methanol and tetrahydrofuran the complex could be isolated as [Pd(Ph2PCH2CH2PPh2)(0C103)2J.
Example 2 Various palladium complexes of the form shown in Formula I above having L3-Y-L4 = 1,2bis(diphenylphosphino)ethane were prepared in situ by the following method.
The complex dichloro 1,2-bis)diphenylphosphino)ethane palladium (ii) and two molar equivalents of the salt silver (i) perchlorate were extensively dried in vacuo and added together in the presence of a donor solvent (where the donor solvent could be acteone, acetonitrile, benzonitrile, o-toluonitrile, methanol, ethanol, tetrahydrofuran or related solvents). After two hours stirring a white precipitate was formed which was filtered off to leave a clear yellow solution containing the complex.
Products prepared by the method in Example 1 were characterised by elemental analysis and/or infra-red spectroscopy and/or proton magnetic resonance spectrometry and/or conductivity measurements. The following table lists typical products obtained together with their characterisation data.
TABLE 1 Products of Example 1 Product No 1 2 3 4 5 Property Ligands Benzonitrile o-Toluonitrile Acetone Water Methanol L3 and L4 (i) %C 50.9(51.7) 53.8(53.8) 41.5(42.2) (ii) %H 4.2(4.1) 4.2(4.1) 3.6(3.8) (iii) %N 3.2(3.3) 2.9(3.0) 0.0(0.0) (iv) B 338 355 - (v) # 307(sh) 310(sh) - - 319 (vi) #(phenyl) - 7.76(7.2)mult - (vii) #(-CH2CH2-) 3.17(1)d - (viii) #(-CH3) 2.31(1.5)s - (ix) 2J(PH) - 25 - (x) # (C N) 2295,2286 2273 (xi) #(C O) 1666 (xii) #(C-C-O) - 1142 - (xiii) AM(MeNO2) - - 185.5 (xiv) #(O-H) - - 3250 (xv) #(H-O-H) - - 1630 - Compound 5 is isolated as [Pd(Ph2CH2CH2Ph2) (OC103)21, identified by its infra-red spectrum, vIOClO3) = 1145 cam~1 (vs), 1020 cm~1 (s,sh), 895 cm~1(s,sh), 620 cm~1(m), 620 cm~1(m). The complex is a non-conductor in dichloroethane solution but an electrolyte (2:1) in methanol solution.
In Properties (i) (ii) and (iii) (TABLE 1) the figures outside the brackets are weight percentages which have been found and the figures inside the brackets are the corresponding calculated values.
In Property (v) Lmax is given by the electronic spectra determined in dichloroethane solution and is measured in nm.
In Properties (vi) (vii) and (viii) 6 is the position of a peak (in parts per million) in the nmr spectrum, s representing a singlet peak, d is a doublet peak and mult a multiplet peak. For Property (vi) the 1 H nmr spectra are determined in d3-nitromethane solution.
In Property (ix) J is the coupling constant measured in Hz between the resonance position of the P and H atoms.
In Properties (x) and (xi) (and xiv)v is the infra-red 'stretching' absorption peak of the given group determined as a nujol mull and measured in um.
In Properties (xii) and (xv) 6 is the infra-red absorbance due to the 'bending' vibration of the given group determined as a nujol mull.
In Property (xiii) AM is the molar conductivity determined in 10-3 M nitromethane solution and measured in ohm-'cm2mol-'.
Example 3 Product No 3 of Example 1 was employed as a catalyst in the hydrogenation of styrene to ethylbenzene.
This was carried out in a glass vessel at room temperature (above 20;C) and with a hydrogen pressure of 1 atmosphere, for about 72 hours. 0.829 of catalyst were used for a styrene weight of 2.089.
The product yield of this reaction was about 99 O. The only by-product, identified by mass-spectral analysis, was a trace of the coupled product C2H.CsH4.C6H4.C2H5. No precipitation or decomposition of the reactants occurred.
These results illustrate the effectiveness of Product No 3 of Example 1 in a hydrogenation reaction.
The catalyst was converted from a pale yellow to a deep red form.
Example 4 Product No 3 of Example 1 was employed as a catalyst in the hydrogenation of oct-1-ene under conditions similar to those of Example 3.
The reaction yield was about 50 O. Traces of oct-2-enes produced during the reaction were found in the product.
Example 5 Product No 5 of Example 1 was employed as a catalyst in the following homogeneous alcoholysis reaction:
(Reaction 1) where pH = phenyl.
This reaction was carried out in a glass vessel at room temperature and atmospheric pressure. The methanol was in excess and 0.779 of catalyst was used per 5.29 oftriphenylsilane.
The reaction occurred steadily and its progress could be monitored by following evoiution of the hydrogen. When this ceased (after about 2 hours), corresponding to an equimolar production of hydrogen with respect to triphenylsilane, furthertriphenylsilane addition produced further smooth evolution of hydrogen as before. The yields obtained were: Ph3SiOCH3 79.80o by weight; Ph3SiOSiPh3 20.2No by weight.
Although this reaction has previously been carried out using various catalysts all previous attempts to use known palladium(ll) complexes have been unsuccessful, ie such complexes were largely inactive.
Example 6 The known complex Pd(dpe)C12, where dpe = 1 ,2-bis(diphenylphosphino)ethane, was used instead of Product No 5 in an attempt to carry out Reaction 1 under conditions similar to those in Example 5.
The known complex was found to be inactive as a cataystforthe reaction. However, addition of two moles of silver perchlorate (for every mole of the known complex) caused the reaction to occur immediately. This was because the known complex in the presence of the perchlorate ions and methanol was converted into a complex embodying the invention and identical to Product No 5 defined above.
Palladium complexes embodying the invention may find use in other reactions involving the hydrogenation of unsaturated organic compounds, eg the conversion of nitrobenzene and its derivatives to the corresponding aniline and derivative forms.
Also, palladium complexes embodying the invention may find use in other alcoholysis reactions such as the reaction of (EtO)3SiH with EtOH, where Et = ethyl.

Claims (13)

1. A palladium complex having a molecular structure:
where L1 and L2 are weakly co-ordinated solvento-ligands and where L3-Y-L4 is a bidentate ligand containing groups L3 and L4 each of which has a Group V or Group VI donor atom attached to the palladium atom, L3-Y-L4 being of the form either R1, R2, R3 and R4 is an optionally substituted alkyl or aryl group, where Y is either (CH2)n, in which n is 1,2 or 3, or o-phenylene, or cis-vinyl, and where each of E1 and E2 is selected from nitrogen, phosphorus, arsenic and antimony and each of E3 and E4 is selected from oxygen, sulphur and selenium, X- being a non-coordinating anion.
2. A palladium complex as claimed in claim 1 and wherein L1 and L2 are independently selected from the following solvento-ligands: acetone, acetonitrile, benzonitrile, o-toluonitrile, methanol, ethanol, tetrahydrofuran and water.
3. A palladium complex as claimed in claim 1 or claim 2 and wherein E1 and E2 are both phosphorus.
4. A palladium complex as claimed in claim 1, claim 2 or claim 3 and wherein R1, R2, R3 and R4 are all phenyl groups.
5. A palladium complex as claimed in any one preceding claim and wherein Y is (CH2)2.
6. A palladium complex as claimed in any one of the preceding claims and wherein X- is ClO4-, BF4 or PF6-.
7. A palladium complex as claimed in claim 1 and which has been prepared by a method substantially the same as Example 1 or Example 2 as described hereinbefore.
8. A method of carrying out an organic reaction in the presence of a catalyst characterised in that the catalyst is a palladium complex as claimed in any one of the preceding claims.
9. A method as claimed in claim 8 and wherein the reaction is a hydrogenation reaction.
10. A method as claimed in claim 9 and wherein the hydrogenation is an alkene hydrogenation.
11. A method as claimed in claim 8 and wherein the reaction is an alcoholysis reaction.
12. A method as claimed in claim 11 and wherein the alcoholysis is of a silane.
13. A method as claimed in claim 8 and which is substantially the same as in Example 3,4, 5 or 6 as described hereinbefore.
GB7929389A 1979-08-23 1979-08-23 Palladium complexes Expired GB2058074B (en)

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EP0170311A2 (en) * 1984-07-30 1986-02-05 Shell Internationale Researchmaatschappij B.V. Process for the dimerization of olefins
EP0220765A1 (en) * 1985-10-15 1987-05-06 Shell Internationale Researchmaatschappij B.V. Novel copolymers of SO2 and ethene
US4740625A (en) * 1986-05-13 1988-04-26 Shell Oil Company Catalyst compositions and a process for polymerizing carbon monoxide and olefins
US4778876A (en) * 1986-05-27 1988-10-18 Shell Oil Company Vapor phase process for polymerizing carbon monoxide and olefins
US4786443A (en) * 1987-03-11 1988-11-22 Shell Oil Company Process for the carbonylation of olefinically unsaturated compounds with a palladium catalyst
US4786714A (en) * 1985-11-29 1988-11-22 Shell Oil Company Catalytic process for polymerizing carbon monoxide and olefin(s) with nitrogen bidentate ligand
US4788279A (en) * 1985-12-10 1988-11-29 Shell Oil Company Catalyst compositions and processes for polymerizing carbon monoxide and olefinically unsaturated hydrocarbons
US4804739A (en) * 1986-07-01 1989-02-14 Shell Oil Company Process for preparing carbon monoxide polymer with quaternary phosphonium compound bidentate ligand
US4806630A (en) * 1986-12-01 1989-02-21 Shell Oil Company Catalytic polymerization of carbon monoxide and olefin, with organo nitro or organo nitrite compound additive
US4808699A (en) * 1986-03-24 1989-02-28 Shell Oil Company Process for preparing polymers of carbon monoxide and ethylene under specified pressures
US4818810A (en) * 1984-10-05 1989-04-04 Shell Oil Company Catalytic process for the preparation of polyketones from carbon monoxide and ethylenically unsaturated hydrocarbon
US4818811A (en) * 1986-10-30 1989-04-04 Shell Oil Company Terpolymer of carbon monoxide and ethylenically unsaturated monomers
US4820802A (en) * 1987-02-03 1989-04-11 Shell Oil Company Improved process of preparing carbon monoxide/olefin copolymer with ortho substituted phosphine catalyst composition.
US4824817A (en) * 1986-12-05 1989-04-25 Shell Oil Company Catalyst for the carbonylation of conjugated dienes
US4824934A (en) * 1986-03-05 1989-04-25 Shell Oil Company Process for polymerizing carbon monoxide with a quinone
US4824935A (en) * 1986-03-05 1989-04-25 Shell Oil Company Process for polymerizing carbon monoxide and olefins with ether
US4831187A (en) * 1985-09-27 1989-05-16 Shell Oil Company Process for the preparation of esters of alpha-ethylenically unsaturated alcohols and alpha-ethylenically unsaturated carboxylic acids
US4831114A (en) * 1986-10-01 1989-05-16 Shell Oil Company Polymerization of carbon monoxide and olefin with acid catalyst
US4831113A (en) * 1986-03-05 1989-05-16 Shell Oil Company Process for polymerizing carbon monoxide and olefins with a quinone
US4835250A (en) * 1983-04-06 1989-05-30 Shell Oil Company Catalytic preparation of polyketone from carbon monoxide and olefin
US4843144A (en) * 1986-08-26 1989-06-27 Shell Oil Company Polymerization of carbon monoxide/olefin with P ligand having polar aryl group
US4851582A (en) * 1986-05-13 1989-07-25 Shell Oil Company Catalyst compositions and a process for polymerizing carbon monoxide and olefins
US4859764A (en) * 1986-08-22 1989-08-22 Shell Oil Company Copolymerization of carbon monoxide and olefin with nitrogen containing phosphine ligand catalyst
US4868282A (en) * 1985-08-25 1989-09-19 Shell Oil Company Polyketone preparation from regulated quotient mixture of olefins
US4873267A (en) * 1987-04-29 1989-10-10 Shell Oil Company Process for the production of methanol and a composition suitable for use as a catalyst in said process
US4880902A (en) * 1987-08-27 1989-11-14 Shell Oil Company Copolymerization of carbon monoxide and olefin with diphosphine having heterocyclic substituents as catalyst
US4970294A (en) * 1988-12-08 1990-11-13 Shell Oil Company α-olefin/carbon monoxide copolymers and catalyst and process for making
US5028734A (en) * 1986-12-10 1991-07-02 Shell Oil Company Process for the selective preparation of alkenecarboxylic acid derivatives
US5436356A (en) * 1993-02-09 1995-07-25 Shell Oil Company Carbonylation process
EP0811629A1 (en) * 1995-02-24 1997-12-10 Nissan Chemical Industries, Limited Optically active bidentate phosphine ligand/palladium complex

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* Cited by examiner, † Cited by third party
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