Abstract
Thermodynamic parameters for bonding a sixth ligand to a number of five coordinate alkylcobalt(III) complexes have been measured. The enthalpies of adduct formation demonstrate the magnitudes of the ground state trans and cis effects in these systems. Substantial differences in the enthalpies of axial bond formation are caused by changes in both the trans and cis ligands. Unusual behavior is observed when tetrahydrofuran and tetrahydrothiophene are the entering ligands. Comparison of the equilibrium constants for these two bases indicates that the cobalt center prefers the more polarizable sulfur donor. On the other hand, the enthalpy measurements show that the metal ligand bond formed is stronger with the oxygen donor. This unusual behavior has been previously observed for the binding of these two bases to methylcobaloxime.
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