Factors affecting the equilibrium constant of homolysis of complexes with metal-carbon σ bonds in aqueous solutions. Pulse radiolysis studies

Pulse-Radiolysis is a powerful technique for the determination of the equilibrium constants of the homolytic cleavage of metal-carbon a bonds in aqueous solutions. In most systems studied the observed reaction is: L_m-1M(ⁿ⁺¹)-R + L === ML_m⁽ⁿ⁾) + R. Therefore the results do not enable a direct determination of the metal-carbon bond dissociation energies. The results obtained indicate that these equilibrium constants are not directly related to the redox potential of either L_mM⁽ⁿ⁾) or of R, or to the activation energies for the homolytic cleavage of a family of similarly substituted ethanes.