Bimolecular substitution and oxidation reactions of 17-electron pentacoordinate metal carbonyl radicals

Summary Quantitative and semiquantitative data for reactions of M₂(CO)_10-2nL_2n (M=Mn or Re; L=P-donor ligand; n=0, 1) are analyzed to provide information regarding the mechanisms and relative rates of substitution and oxidation reactions of the M(CO)_5-nL_n] radicals. Both associative and dissociative paths for substitution can be inferred, but the dissociative paths are generally much slower and occur only at high temperatures and/or when associative substitution is sterically disfavoured. Quantitative comparison of the reactivities of various radicals is made.