The First Photocrystallographic Evidence for Light-Induced Metastable Linkage Isomers of Ruthenium Sulfur Dioxide Complexes

Light-induced metastable linkage isomers of trans-Ru(NH(3))(4)Cl(SO(2))Cl and trans-Ru(NH(3))(4)(H(2)O)(SO(2))(C(6)H(5)SO(3))(2) have been identified for the first time using photocrystallographic methods. In both linkage isomers the SO(2) ligand is side bound, but the Ru-O and Ru-S distances are considerably longer and almost equal in the trans-H(2)O isomer. DFT calculations confirm that both isomers correspond to minima on the ground-state potential energy surface and also predict the existence of a second oxygen-bound isomer for both compounds. The decay of the light-induced species has been studied by both DSC and IR. Activation energies for the thermal back-reaction, as derived from the temperature-dependent disappearance of light-induced IR bands, are 50.0 and 58.4 kJ/mol for the two isomers, which is larger than the corresponding numbers for photoinduced side-bound nitrosyl linkage isomers.