The kinetics and mechanism of diene exchange in (η4-enone) Fe(CO)2L complexes (L = phosphine,phosphite) |
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| Authors: | James AS Howell John C Kola Denis T Dixon Philip M Burkinshaw Marion J Thomas |
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| Institution: | Chemistry Department, University of Keele, Keele, Staffordshire ST5 5BG Great Britain |
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| Abstract: | 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. |
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| Keywords: | To whom correspondence should be addressed |
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