Abstract
Irradiation of Ru( η 6-mes) 2 2+ (mes is 1,3,5-trimethylbenzene, or mesitylene) in acetonitrile results in the substitution of one mesitylene ring by solvent to yield the half-sandwich complex, Ru( η 6-mes)(CH 3CN) 3 2+. The quantum efficiency of this process exhibits little dependence upon the excitation wavelength or the presence of oxygen, but varies with solvent in the order acetonitrile > water > acetone. Photolysis of Ru( η 6-mes)(CH 3CN) 3 2+ in acetonitrile occurs via two competing pathways: substitution of mesitylene by solvent to produce Ru(CH 3CN) 6 2+, and exchange of coordinated CH 3CN with bulk solvent. Quantum efficiencies for both pathways increase with decreasing excitation wavelength and, at each wavelength, CH 3CN exchange is more efficient than mesitylene substitution. Photochemical mechanisms for these processes are discussed and comparisons with related complexes are presented.
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