Di- and tri-nuclear ruthenium nitrosyl complexes containing thiolate ligands

Abstract

Treatment of Ru(NO)Cl3 with NaSC6F4H (C6F4HSH = 2,3,5,6-tetrafluorothiophenol) afforded the hydroxo-bridged dimer Na(H2O)2[Ru(NO)(SC6HF4)2]2(μ-SC6HF4)2(μ-OH) (Na(H2O)21), in which the {Na(H2O)2}+ moiety binds to the diruthenium core via the μ-hydroxo ligand and three ortho fluorine atoms of the thiolate ligands. Metathesis of Na(H2O)21 with Bun4NBr and Ph4PCl afforded Na-free (Bun4N)[1] and (Ph4P)[1], respectively. Treatment of Ru(NO)Cl3 with NaSBut afforded the trinuclear oxo-sulfido cluster Na(H2O)2[Ru(NO)(SBut)(μ-SBut)]3(μ3-S)(μ3-O) (Na(H2O)22) that contains a trinuclear {Ru3(SBut)3} core capped by a μ3-oxo and a μ3-sulfido ligand. The {Na(H2O)2}+ moiety binds to the triruthenium core via the μ3-oxo and two terminal thiolate ligands. Metathesis of Na(H2O)22 with Bun4NBr gave (Bun4N)[2]. Treatment of Ru(NO)Cl3 with NaStipp (tipp = 2,4,6-triisopropylphenyl) gave mononuclear Ru(NO)(Stipp)3(tippSH) (3). The crystal structures of Na(H2O)21, (Ph4P)[1], and Na(H2O)22 have been determined.