Session: Coordination Chemistry: Synthesis and Characterization:

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.

Dustin Pumford

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