Abstract
Treatment of [Ru(PPh3)3Cl2] or [RuHCl(CO)(PPh3)3] with 1-(4-chlorophenyl)imidazole-2-thione (HtimAr) in tetrahydrofuran (THF) at reflux afforded the mononuclear complex [Ru(κ1-S-HtimAr)2(PPh3)2Cl2] (1) and [RuH(CO)(κ1-S-HtimAr)(PPh3)2Cl] (4), respectively, whereas interaction of [Ru(PPh3)3Cl2] or [RuHCl(CO)(PPh3)3] with HtimAr in the presence of NaOMe in THF gave the mononuclear complex cis-[Ru(κ2-S,N-timAr)2(PPh3)2] (2) and [RuH(CO)(κ2-S,N-timAr)(PPh3)2] (5), respectively. Reaction of [RuCl2(PPh3)3] with 1 equiv. of HtimAr in the presence of Et3N and H2O2 gave a Ru(III) complex, [Ru(κ2-S,N-timAr)(PPh3)2Cl2] (3). Reaction of [(η6-p-cymene)RuCl(μ-Cl)]2 with HtimAr in THF at reflux in the presence of NaOMe and K[PF6] gave the μ-S,N-timAr-bridged dinuclear complex [{(η6-p-cymene)Ru}2{μ-η1(S), η1(N)-timAr}{μ-η2(S), η1(N)-timAr}{κ1-S-HtimAr}][PF6]2 (6). Reaction of [RuHCl(CO)(PPh3)3] or [Ru(PPh3)3Cl2] with the bulky ligand [HB(timAr)3]− at reflux resulted a ruthenaboratrane complex, [Ru(CO){κ4-B,S,S,S-B(timAr)3}(PPh3)] (7) and a typical Ru⋯H–B complex, [Ru{κ3-H,S,S-HB(timAr)3}(κ2-S,N-timAr)(PPh3)] (8), respectively. All complexes have been spectroscopically and electrochemically characterized. The structures of 1·CH2Cl2, 2, 3·CH2Cl2, 4·C6H14, 6, 7·CH3OH·0.5H2O, and 8·0.5C6H14·0.5CH2Cl2·2H2O have also been determined by single-crystal X-ray diffraction.
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