Compounds of the type Ru(NO)(Schiff base)(X) and [Ru(NO)(Schiff base)(L)]Y, where Schiff base = tBu4Salchy and tBu4Saloph (tBu4Salchy = (R,R/S,S)-N,N′-Bis(3,5-di-tert-butylsalicylidene)-1,2- cyclohexanediamine, tBu4Saloph = N,N-Bis(3,5-di-tert-butylsalicylidene)-1,2- diaminobenzene; L = 1-methylimidazole, H2O; X = methoxide, substituted phenoxides; Y = CF3SO3- or BF4-) were synthesized, characterized, and their redox properties evaluated (spectro)electrochemical methods. The X and L ligands are located trans- to the NO ligand in these octahedral complexes. Complexes were characterized by 1H and 13C NMR, IR, and in some cases single crystal X- ray diffraction. Cyclic voltammetry studies were used to explore the redox properties of these models, while infrared spectroelectrochemistry was used to identify reduction and oxidation products in situ. The complexes prepared in this study show a correlation between the electron density of the X or L ligand and the stretching vibration of the trans- nitrosyl ligand. The [Ru(NO)(Schiff base)H2O]BF4 complexes were also synthesized and can the aquo-cation be observed by after oxidation of other Ru(NO)(Schiff base)(X) species by fiber-optic IR spectroelectrochemistry in the presence of adventitious moisture.

Synthesis, characterization and (spectro)electrochemistry of Schiff base nitric oxide complexes of ruthenium

ACS Spring Meeting 2021

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