Unravelling the kinetics of electro- and photochemical S → O linkage isomerization in Ru(II)-NHC-DMSO complexes utilised for photoinduced substitution reactions.

Our recently reported Ru(III)-NHC complexes 1a and 1b were utilized as suitable precursors to prepare new Ru(II)-NHC-(DMSO) 2 complexes 2a and 2b. Complexes 2a and 2b reacted with 2,2'-bipyridine to give complexes 3a and 3b, respectively, with substitution of only one of the DMSO ligands. All new complexes were characterized using various spectroscopic techniques and the molecular structures of 2a and 3a were determined using single-crystal X-ray diffraction technique. Complexes 2a, 2b, 3a, and 3b showed the S → O linkage isomerization of the DMSO ligand upon oxidation of the Ru centre from +II to +III, as confirmed by the thermodynamic and kinetic data obtained from cyclic voltammetry experiments. It was observed that in the bisdimethylsulfoxide complexes 2a and 2b, only one DMSO ligand isomerized, which was further corroborated by the computational studies performed to optimize the geometry of the possible linkage isomers of complexes 2a and 3a in +2 and +3 oxidation states, whereas complexes 3a and 3b showed a high preference for the O-bound isomer in the Ru(III) redox state. The role of NHC in stabilizing the mixed isomer in complexes 2a and 2b and preventing the isomerization of both DMSO ligands coordinated to the Ru centre was studied; moreover, NHC provided good solvent compatibility for photochemical S → O isomerization in all the complexes. Taking advantages of the photoinduced linkage isomerization in 2a and 2b, the synthesis of 3a and 3b was revisited and performed using 2a and 2b, respectively, following a photoinduced substitution reaction in the presence of 2,2'-bipyridine. The kinetics of the reversion from the O-bound to S-bound isomer was found to follow the DMSO-assisted intermolecular S → O isomerization pathway.