The Cr(II) reduction of Co(ptdn)3 was studied in various dimethylformamide/water mixtures at μ = 1.00 M (CH3COOLi). The activation parameters were measured over a temperature range of 25-45°C. Three pathways for reduction were observed-outer sphere, monobridged inner sphere, and dibridged inner sphere. Only the dibridged pathway showed an acid dependence. The outer-sphere and monobridged inner-sphere routes followed simple second-order kinetics whereas the dibridged path showed evidence for the presence of a binuclear intermediate. It was postulated that the dibridged transition state was stabilized by an organic solvent cage.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry