Synthesis, Structure, and Redox Properties of a New Aqua Ruthenium Complex Containing the Tridentate [9]aneS3 and the Didentate 1,10‐Phenanthroline Ligands

Abstract
The synthesis of a new Ru−H2O complex [Ru(phen)(H2O)([9]aneS3)](ClO4)2, 2, (phen = 1,10‐phenanthroline, [9]aneS3 = 1,4,7‐trithiacyclononane) is described. The complex is characterized by UV/Vis and 1‐D and 2‐D NMR spectroscopy in solution. The complex has been further characterized in the solid‐state by X‐ray diffraction analysis which displays a distorted octahedral coordination geometry around the Ru metal center. The cyclic voltammetric experiments of the complex show a pH‐dependent chemically irreversible wave at Ep,a = 0.82 V, at pH = 7.0, indicating the low stability of the higher oxidation states. Nevertheless, before the complex decomposes, it is capable of electrocatalytically oxidizing benzyl alcohol (BzOH) to benzaldehyde with a second‐order rate constant of 19.8 M−1s−1. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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