Substituted [Ru(saloph)(NO)Cl] (N,N′-bis-(salicylidene)-o-phenyldiamine) and related complexes have been synthesized and characterized spectroscopically. Their electrochemical reactivity is reported herein. In the parent complexes [Ru(saloph)(NO)Cl], the nitrosyl ligand is linear with the ligand acting formally as NO+. The complexes are observed to undergo two metal-based reductions by cyclic voltammetry, which are amenable to mechanistic study. The initial reduction to the corresponding anion promotes a change in the nitrosyl ligand from a linear to bent geometry, observable by IR spectroscopy. In coordinating solvents, the reduction is initiates Cl- ligand metathesis for solvent, resulting in the formation of a neutral solvent-coordinated {RuNO}7 species. This chloride loss is shown to be reversible in the presence an added chloride source and values of the equilibrium constant and rate constant for chloride loss have been estimated. The neutral solvent coordinated species can be detected spectroscopically by IR, EPR and visible spectroscopies. The second reduction results in the formation of an anionic {RuNO}8 species. The reactivity of these reduced species with H-atom sources and H+ sources has been investigated.

Electrochemical investigation of [Ru(saloph)(NO)(Cl)]-type complexes (saloph = N,N′-bis-(salicylidene)-o-phenyldiamine, and derivatives)

255th National Meeting (2018)

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