Kinetics of nucleophilic attack on co-ordinated organic moieties. Part 7. Mechanisms of addition of tertiary phosphines and phosphites to tricarbonyl(dienyl)iron cations
- 1 January 1979
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 5,p. 873-878
- https://doi.org/10.1039/dt9790000873
Abstract
The reaction of tertiary phosphines and phosphites with dienyl complexes such as [Fe(C6H7)(CO)3][BF4](1) provides a general route to phosphonium adducts of the type [Fe(C6H7·PR3)(CO)3][BF4](R = Ph, p-tolyl, Bun, OPh, or OBun). An analogous reaction with 1,2-bis(diphenylphosphino)ethane leads to the dimeric salt [Fe2{( C6H7·Ph2PCH2)2}(CO)6][BF4]2. The rate law, Rate =k[Fe][PR3], is observed for addition of a range of phosphines and phosphites to (1) and the related cations [Fe(C6H6OMe)(CO)3]+ and [Fe(C7H9)(CO)3]+. Rate and activation parameters indicate direct addition at the dienyl rings. The marked dependence of k on the basicity of phosphorus nucleophiles suggests significant bond making in the transition states for adduct formation.Keywords
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