Abstract
Variable temperature and pressure 13C NMR measurements have been used to study the kinetics of solvent exchange of the five coordinate complexes of Co(II) and Ni(II) with 1,4,8,11-tetramethyl-1,4,8, 11-tetraazacyclotetradecane in acetonitrile. While the activation volume value of −9.6 ± 0.5 ml mol −1 supports the proposal of an associative interchange, I a, mechanism for the Co(II) system, the value of +2.3 ± 1.3 ml mol −1 for the Ni(II) system suggests a dissociative, D, mechanism. UV-visible spectral measurements of the Ni(II) complex in acetronitrile over a range of temperatures are consistent with the presence of an equilibrium involving the five coordinate and a square planar form of the complex. It is proposed that the solvent exchange on the five coordinate Ni(II) complex takes place via this four coordinate species.
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