Kinetic study of the reaction of ferrocenes and ferrocenium ions with ground and excited states of tris(2,2-bipyridine)chromium ions and the preparation and homolysis of organocobalt complexes.

摘要

The kinetics of quenching of *Cr(bpy)(sub 3)(sup 3+) by d(sup 6) metallocenes and by ferrocenium ions were studied by laser flash photolysis. The quenching by ferrocenium ions proceeds by energy transfer and is dependent on the donor-acceptor distance, as expected for an electron-exchange mechanism. The rate constants for quenching with d(sup 6) metallocenes are at or near the diffusion-controlled limit. The reactions partition themselves between electron transfer and energy transfer. The preparations of a series of organocobalt complexes, RCo(Me(sub 6)(14)4,11-dieneN(sub 4))(sup 2+) and RCo(Me(sub 6)(14)aneN(sub 4))(sup 2+)(R = primary and substituted primary alkyl group), are presented. The complexes were characterized by (sup 1)H NMR spectroscopy, UV-visible spectroscopy and a crystal structure determination for ClCH(sub 2)Co(Me(sub 6)(14)4,11-dieneN(sub 4))(H(sub 2)O)(ClO(sub 4))(sub 2). the unimolecular homolysis have been studied for some of these complexes. 89 refs., 14 figs., 20 tabs. (ERA citation 15:035198)