Synthesis, structure, and electrochemistry of mer-[RuCl_3(DMSO-S)(DMSO-O)(py)]

摘要

Reaction of mer-[RuCl_3(DMSO-S)_2(DIVISO-O] (1) with pyridine (py) in dichloromethane yields mer-[RuCl_3(DMSO-S)(DMSO-O)(py)] (2). A single crystal suitable for X-ray diffraction was obtained by recrystalization with dichloromethane and diethyl ether. X-ray diffraction analysis revealed an unusual case in which two independent molecules (2a and 2b) are present in the asymmetric unit cell. Both molecules have distorted octahedral geometry in which DMSO is bound through oxygen and sulfur. Density functional theory (DFT) calculations were performed for 2a and 2b in gas phase to investigate bonding shown by the two DMSO ligands. Optimizations were done on both DMSO ligands bonded through S, both DMSO ligands bonded through O, one DMSO bonded through O, and the other through S but opposite to the actual molecule. The energy differences of the optimized structures were calculated.