Electrochemical Investigations of Ru(L)(NO)(OPh) and Related Derivatives (L = Porphyrin or Bis(salicyl)Diiminate Ligand)

A set of porphyrin and non-porphyrin complexes Ru(por)(NO)(OAr) and Ru(sal)(NO)(OAr’) complex have been prepared and studied by electrochemical and spectroelectrochemical methods (por = octaethylporphyrin, Ar = Ph, C 6 H 4 -2-NHC(=O)CF 3 ; C 6 H 3 -2,6-(NHC(=O)CF 3 ) 2 , sal = racemic (R,R/S,S)-N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2- cyclohexanediamine, N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminobenzene; Ar’ = OPh, p -C 6 H 4 CF 3 ). The consequence of 1-electron oxidation is loss of the aryloxide ligand, however the mechanism of that loss depends on the specific aryloxide ligand present in the complex. This conclusion is supported by cyclic voltammetry, DigiElch simulations, chemical oxidation studies, EPR spectroelectrochemistry and in-situ fiber-optic infrared spectroelectrochemistry measurements.