Effect of Solvent on the Reactions of Coordination Complexes. Part 22.1 Kinetics of Base Hydrolysis of Some (Aminomonocarboxylato)(tetraethylenepentamine)cobalt(III) Complexes in Acetonitrile–Water Media: the Role of Solvent Basicity and Solvent Structure

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Anadi C. Dash and Smrutiparava Das


Abstract

The base of hydrolysis of [(tetren)CoO2CR]2+ {R=NH2CH2—, NH2[CH2]2—, pyridine-2- (αβS isomer), NH2CH(CH3)— (αβS and αβR isomers); tetren=tetraethylenepentamine} is accelerated by acetonitrile+water media (0≤XAN≤0.578, XAN=mole fraction of acetonitrile) owing to the combined effects of destabilisation of OH-, relatively greater destabilisation of the transition state of the amido conjugate base [((tetren)-H)Co2+[triple bond, length as m-dash]-O2 CR]+* as compared to that of the initial state [(tetren)CoO2CR]2+, and solvent structure; the activation enthalpies and entropies are also sensitive to solvent structure and conformational arrangement of the tetren ligand.


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