Metal carbonyls. V. Kinetics of the reaction of monosubstituted manganese pentacarbonyl bromides with a variety of reagents

Article abstract of DOI:10.1021/ic50008a014

The rates of reaction of Mn(CO)₄LX with a variety of reagents L′ to form Mn(CO)₃LL′X were found to be independent of the nature and concentration of L′, but to decrease with increasing atomic number of X and also to decrease with changes in L in the following order: P(C₆H₅)₃ > As(C₆H₅)₃ > P(C₄H₉)₃ ～ P(C₆H₅)₂Cl > P(OC₆H₅)₃ ～ Sb(C₆H₅)₃ > P(C₆H₅)Cl₂ ～ P(OC₄H₉)₃ > P(OCH₂)₃CCH₃ (the group C₄H₉ is n-butyl). These results have been interpreted as indicating a dissociation mechanism in which the bulkiness of L determines the rate of CO dissociation. The absorption maxima of several Mn(CO)₄LBr complexes in the near-ultraviolet region also are reported.