Adducts of ruthenium(IV) thiolates with substituted pyridines. Syntheses and structures of [Ru(SMes)4(R-py)] (R = 4-Et, 4-tBu, and 3,5-Me2) and [{Ru(SMes)4}2(μ-4,4’-bipy)] (Mes = 2,4,6-trimethylphenyl)

Abstract

Treatment of the trigonal-bipyramidal ruthenium(IV)–thiolate complex, [Ru(SMes)4(MeCN)] (Mes = 2,4,6-trimethylphenyl, 1), with an anhydrous diethyl ether solution of hydrogen chloride in THF afforded [Ru(SMes)3Cl(MeCN)] (2), whereas interaction of 1 with [Et4N]Cl in THF gave an anionic ruthenium(IV)–thiolate complex, [Et4N][Ru(SMes)4Cl] (3). Reaction of 1 with one equivalent of substituted pyridines in dichloromethane gave the corresponding pyridine-coordinated ruthenium(IV)–thiolate complexes, [Ru(SMes)4(R-py)] (R = 4-Et, 4; 4-tBu, 5; 3,5-Me2, 6), while reaction of 1 with 0.5 equiv. of 4,4’-bipy (4,4’-bipy = 4,4’-bipyridine) in dichloromethane resulted in the formation of a dinuclear ruthenium(IV)–thiolate complex [{Ru(SMes)4}2(μ-4,4’-bipy)] (7). Complexes 2–7 have been spectroscopically characterized along with their electrochemical analyses, and their structures have been determined by single-crystal X-ray diffraction.