Synthesis, crystal structure and redox properties of µ-oxo-bis(µ-acetato)-diruthenium(III) complexes having 2,2′-bipyridine and imidazole bases as terminal ligands
Abstract
Three diruthenium(III) complexes, [{Ru(bipy)L}2(µ-O)(µ-O2CMe)2][ClO4]2, have been prepared and characterized (L = imidazole, 1- or 4-methylimidazole; bipy = 2,2′-bipyridine). The crystal structure of the 1-methylimidazole complex [Ru2O(O2CMe)2(bipy)2(1-mim)2][ClO4]2·H 2O·MeOH has been determined. The complex has a Ru2(µ-O)(µ-O2CMe)22+ core with terminal unidentate 1-mim and bidentate chelating bipy ligands. The imidazole is trans to the oxide ligand. The Ru ⋯ Ru distance and Ru–O–Ru angle are 3.285(2)Å and 121.5(3)°. The 1H NMR spectra of the complexes are consistent with this crystal structure. The complexes show an intense charge-transfer band near 600 nm. They are redox active and display reversible one-electron oxidation and reduction processes. On addition of weak proton-donor imidazole bases the complexes undergo a one-step two-electron reduction process RuIIIRuIII–RuIIRuII along with the RuIIIRuIII–RuIIIRuIV oxidation couple.
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