Abstract

Binding constants for eight axial ligands, including four primary amines, and CN, SCW, N02, and N3, to m-and p- carbomethoxyphenyl (aquo)cobaloximes have been determined in aqueous solution at 25.0 C, ionic strenght 1.0 M. These constants have been used to establish experimental conditions for the measurement of the second-order rate constants for base-catalyzed hydrolysis of these cobaloxime substituted methyl benzoates. These rate constants have been correlated via the Taft dual substituent parameter equation to provide values for the inductive and resonance substituent constants for the ehelated substituents -Co(D2H2)L. The results show that substantial resonance interaction can occur between these substituents and carbomethoxyphenyl-organic ligands when L is an unsaturated inorganic ligand capable of ir-interactions with the cobalt atom. Inductive electron donation by the substituent -Co(D2H2)L is found to increase linearly with proton basicity of L for all the inorganic ligands save on, while an unexpected inverse dependence is seen for L= RNH2.

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