Anadi C. Dash and Smrutiparava Das
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+-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.