Abstract
Stability and rate constants as well as activation parameters have been determined for the reactions of cobalt(III)tetra(N-methylpyridyl)porphine with thiocyanate ion as a function of pH. The porphyrin ligand increases the substitution rates at the metal center by several orders of magnitude relative to most other cobalt(III) complexes. The rates of formation and dissociation of the thiocyanate complexes are also dependent on the nature of the axial ligand (water, hydroxide or thiocyanate) trans to the leaving group. A bound thiocyanate ion labilizes the remaining water molecule by a factor greater than 10 4 and also changes the p K a of this group by at least three log units.
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