화학공학소재연구정보센터
Inorganic Chemistry, Vol.36, No.24, 5432-5434, 1997
Inter-metal nitrogen atom transfer reactions between nitridochromium(V) and chromium(III) porphyrins
Reactions of nitridochromium(V) porphyrins with chromium(III) porphyrins resulted in reversible, infer-metal nitrogen atom transfer between the two chromium porphyrin complexes. The progress of these reactions was followed spectrophotometrically. Kinetic analysis of the spectral data obtained over time for a variety of substituted porphyrins showed the reactions to be first order in each of the reactants and second order overall. Equilibrium constants were computed from the spectral data and ranged from 0.56 to 2.1 for the reactions between nitridochromium(V) octaethylporphyrin and a series of chlorochromium(III) tetraphenylporphyrins possessing phenyl ring substituents, Forward rate constants were determined for this reaction series and ranged from 6.8 to 1420 M-1 s(-1) Electron-withdrawing substituents enhanced the forward rates but diminished the equilibrium constants. It is proposed that the reactions proceed by nucleophilic attack of the nitridochromium porphyrin donor on the cationic chromium(III) porphyrin nitrogen atom acceptor facilitating a net, two-electron redox process mediated by a homobimetallic mu-nitrido intermediate.