Add time:08/16/2019         Source:sciencedirect.com

The redox-active bis-chelate hexacoordinate ruthenium complex 2 Ru(ONO)2 comprising two redox-active 2,4,6,8-tetrakis(tert.-butyl)-9-hydroxyphenoxazin-1-one ligands 1 was synthesized by coupling ruthenium trichloride with 1 or its thallium salt. Reduction of 2 with zinc amalgam produces its radical-anion 2a, which readily reacts with pyridine in aerobic conditions resulting in substitution of one of the tridentate hydroxyphenoxazinone ligand by three pyridine molecules and the formation of a salt of tris(pyridine)(tetra-(tert.-butyl)oxyphenoxazin-1-onate) Ru(II) cation 5. The structure of this salt was established by X-ray crystallography and its redox activity investigated using cyclic voltammetry. The mechanism of the RuIII/RuII conversion observed in this reaction was suggested based on the data of ESR, UV-Vis spectra and DFT B3LYP/6-311++G(d,p)/SDD calculations.

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