The reactions of platinum(O) and palladium(O) tertiary phosphine complexes with phenyl dicyanooxiranes

Robert B. Osborne; James A. Ibers

doi:10.1016/S0022-328X(00)89217-7

The reactions of platinum(O) and palladium(O) tertiary phosphine complexes with phenyl dicyanooxiranes

Robert B. Osborne^*, James A. Ibers

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

10 Scopus citations

Abstract

The phenyldicyanooxiranes, trans-2,3-dicyano-2,3-diphenyloxirane, 2,2-dicyano-3,3-diphenyloxirane, and 2,2-dicyano-3-phenyloxirane, are cleaved by platinum(O) tertiary phosphine complexes to afford zerovalent metal-olefin complexes and phosphine oxides. The π-olefin products were characterized by ¹H and ³¹P ¹H NMR spectroscopy and by an X-ray structure determination of Pt[trans-Ph(CN)CC(CN)Ph](PPh₃)₂·CH₃OH. Deoxygenation of the ring proceeds with retention of configuration in the final two-carbon olefin fragment. The π-complex Pt[Ph₂CC(CN)₂](PPh₃)₂ is isolable, but the olefin dissociates in the presence of alternative ligands. While Pd[Ph(H)CC(CN)₂](PPh₃)₂ may be isolated, the analogous complex with Ph₂CC(CN)₂ cannot be.

Original language	English (US)
Pages (from-to)	371-385
Number of pages	15
Journal	Journal of Organometallic Chemistry
Volume	232
Issue number	4
DOIs	https://doi.org/10.1016/S0022-328X(00)89217-7
State	Published - Jul 6 1982

Funding

We are gratefui to Dr. T.H. Tulip for his initial work in this area and for crystals of Pt[ trans-Ph(CN)CC(CN)Ph] (PPh& - MeOH. We also thank Dr. G.B. Jameson for his help. This work was supported by the National Science Foun-daticon (CHESO-09671). We thank Johnson-Matthey, Inc. of Malvern, Pennsylvania for the loan of platinum and palladium starting materials.

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/S0022-328X(00)89217-7

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title = "The reactions of platinum(O) and palladium(O) tertiary phosphine complexes with phenyl dicyanooxiranes",

abstract = "The phenyldicyanooxiranes, trans-2,3-dicyano-2,3-diphenyloxirane, 2,2-dicyano-3,3-diphenyloxirane, and 2,2-dicyano-3-phenyloxirane, are cleaved by platinum(O) tertiary phosphine complexes to afford zerovalent metal-olefin complexes and phosphine oxides. The π-olefin products were characterized by 1H and 31P 1H NMR spectroscopy and by an X-ray structure determination of Pt[trans-Ph(CN)CC(CN)Ph](PPh3)2·CH3OH. Deoxygenation of the ring proceeds with retention of configuration in the final two-carbon olefin fragment. The π-complex Pt[Ph2CC(CN)2](PPh3)2 is isolable, but the olefin dissociates in the presence of alternative ligands. While Pd[Ph(H)CC(CN)2](PPh3)2 may be isolated, the analogous complex with Ph2CC(CN)2 cannot be.",

author = "Osborne, {Robert B.} and Ibers, {James A.}",

note = "Funding Information: We are gratefui to Dr. T.H. Tulip for his initial work in this area and for crystals of Pt[ trans-Ph(CN)CC(CN)Ph] (PPh& - MeOH. We also thank Dr. G.B. Jameson for his help. This work was supported by the National Science Foun-daticon (CHESO-09671). We thank Johnson-Matthey, Inc. of Malvern, Pennsylvania for the loan of platinum and palladium starting materials. Copyright: Copyright 2014 Elsevier B.V., All rights reserved.",

year = "1982",

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doi = "10.1016/S0022-328X(00)89217-7",

language = "English (US)",

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pages = "371--385",

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T1 - The reactions of platinum(O) and palladium(O) tertiary phosphine complexes with phenyl dicyanooxiranes

AU - Osborne, Robert B.

AU - Ibers, James A.

N1 - Funding Information: We are gratefui to Dr. T.H. Tulip for his initial work in this area and for crystals of Pt[ trans-Ph(CN)CC(CN)Ph] (PPh& - MeOH. We also thank Dr. G.B. Jameson for his help. This work was supported by the National Science Foun-daticon (CHESO-09671). We thank Johnson-Matthey, Inc. of Malvern, Pennsylvania for the loan of platinum and palladium starting materials. Copyright: Copyright 2014 Elsevier B.V., All rights reserved.

PY - 1982/7/6

Y1 - 1982/7/6

N2 - The phenyldicyanooxiranes, trans-2,3-dicyano-2,3-diphenyloxirane, 2,2-dicyano-3,3-diphenyloxirane, and 2,2-dicyano-3-phenyloxirane, are cleaved by platinum(O) tertiary phosphine complexes to afford zerovalent metal-olefin complexes and phosphine oxides. The π-olefin products were characterized by 1H and 31P 1H NMR spectroscopy and by an X-ray structure determination of Pt[trans-Ph(CN)CC(CN)Ph](PPh3)2·CH3OH. Deoxygenation of the ring proceeds with retention of configuration in the final two-carbon olefin fragment. The π-complex Pt[Ph2CC(CN)2](PPh3)2 is isolable, but the olefin dissociates in the presence of alternative ligands. While Pd[Ph(H)CC(CN)2](PPh3)2 may be isolated, the analogous complex with Ph2CC(CN)2 cannot be.

AB - The phenyldicyanooxiranes, trans-2,3-dicyano-2,3-diphenyloxirane, 2,2-dicyano-3,3-diphenyloxirane, and 2,2-dicyano-3-phenyloxirane, are cleaved by platinum(O) tertiary phosphine complexes to afford zerovalent metal-olefin complexes and phosphine oxides. The π-olefin products were characterized by 1H and 31P 1H NMR spectroscopy and by an X-ray structure determination of Pt[trans-Ph(CN)CC(CN)Ph](PPh3)2·CH3OH. Deoxygenation of the ring proceeds with retention of configuration in the final two-carbon olefin fragment. The π-complex Pt[Ph2CC(CN)2](PPh3)2 is isolable, but the olefin dissociates in the presence of alternative ligands. While Pd[Ph(H)CC(CN)2](PPh3)2 may be isolated, the analogous complex with Ph2CC(CN)2 cannot be.

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The reactions of platinum(O) and palladium(O) tertiary phosphine complexes with phenyl dicyanooxiranes

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