The kinetics and mechanism of diene exchange in (η4-enone) Fe(CO)2L complexes (L = phosphine, phosphite)

Autor:	John C. Kola, Marion J. Thomas, Philip M. Burkinshaw, James A. S. Howell, Denis T. Dixon
Rok vydání:	1984
Předmět:	Steric effects Reaction mechanism Diene Chemistry Stereochemistry Organic Chemistry Kinetics Enantioselective synthesis Biochemistry Medicinal chemistry Inorganic Chemistry chemistry.chemical_compound Materials Chemistry Physical and Theoretical Chemistry Enone Phosphine
Zdroj:	Journal of Organometallic Chemistry. 266:83-96
ISSN:	0022-328X
DOI:	10.1016/0022-328x(84)80113-8
Popis:	Kinetic data for the exchange of 1,3-cyclohexadiene with (η4-benzylideneacetone)Fe(CO)2L complexes (L = CO, PPh3-xMex (x = 0-2) or P(OPh)3) to give (η4-1,3-cyclohexadiene)Fe(CO)2L derivatives indicate a mechanism involving stepwise competing D and Id opening of the ketonic M-CO π-bond. Rates increase in the order CO ⪢ PPh3 ≈ P(OPh)3 > PPh2Me ⪢ PPhMe2, and both steric and electronic factors appear to be important. (η4-1,3-cyclohexadiene)Fe(CO)2L complexes of potential use in enantioselective synthesis (L=(+)-Ph2P(menthyl) or (+)-Ph2PCH2CH(Me)Et) may be prepared via their (η4-benzylideneacetone)Fe(CO)2L complexes.
Databáze:	OpenAIRE
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