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Remarkable differences in catalyst activity and selectivity for the production of methyl propanoate versus CO-ethylene copolymer by a series of palladium complexes of related C4-bridged diphosphines

Lookup NU author(s): Dr Julian Knight, Dr Simon DohertyORCiD, Emeritus Professor Anthony Harriman


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The C4-bridged diphosphines cis- and £ra7zs-l,2-bis(diphenylphosphinomethyl)cyclohexane (cis, la; trans, Ib) and e;zrfo,e7zrfo-2,3-bis(diphenylphosphinomethyl)norbornane and exo,enrfo-2,3-bis(diphenylphosphinomethyl)norbornane (endo,endo, le; exo,endo, Id) and their corresponding palladium complexes [(P-P)PdCl2] (2a-d), [(P-P)Pd(OAc)2] (3a-d), and [(P-P)PdMeCl] (P-P = la, 4a; P-P = le, 4c) have been prepared and characterized. Singlecrystal X-ray analysis of 2a reveals that la forms a seven-membered chelate ring with the ci's-disubstituted cyclohexyl ring in the expected chair conformation. Variable-temperature 31P{1H} NMR studies of 2a have revealed a dynamic process that interchanges stereoisomers via conformational changes in the six-membered ring, often characteristic of c/s-disubstituted cyclohexane derivatives. © 2000 American Chemical Society.

Publication metadata

Author(s): Knight JG, Doherty S, Harriman A

Publication type: Article

Publication status: Published

Journal: Organometallics

Year: 2000

Volume: 19

Issue: 24

Pages: 4957-4967

Print publication date: 27/11/2000

ISSN (print): 0276-7333

ISSN (electronic): 1520-6041

Publisher: American Chemical Society


DOI: 10.1021/om000688o


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