Ruthenium dinitrosyl complexes – computational characterization of structure and reactivity

Elucidation of the electronic structure of a dinitrosyl dithiolate ruthenium complex in several formal oxidation states ranging from Ru(I) to Ru(III) has been undertaken. DFT and ab initio molecular dynamics simulations have shown clear evidence of asymmetry within the dinitrosyl moieties in all models though most noticeably in the excited states. The reaction pathway of a hyponitrite adduct formation was also examined and found to be more feasible in the excited states. These results, along with the recently reported study on the dinitrosyl dithiolate iron analog of these complexes, provide insight toward the mechanism of NO donation by dinitrosyl metal complexes.