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Ruthenium Complexes with Dithiophosphonates [Ar(RO)PS2] and [Fc(RO)PS2] (Ar = p-CH3OC6H4, Fc = Fe(η5-C5H4)(η5-C5H5))

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posted on 28.06.2010, 00:00 by Xi-Ying Wang, Yan Li, Qing Ma, Qian-Feng Zhang
Treatment of dimeric [(η6-p-cymene)RuCl(μ-Cl)]2 with Lawesson’s reagent [ArP(S)(μ-S)]2 (Ar = p-C6H4OMe) in THF gave [(η6-p-cymene)Ru{μ-η1(S),η2(S,S′)-ArP(S)S2}]2 (1) as the sole isolable product. The chlorides in the starting ruthenium compound were substituted by [ArP(S)S2]2− as a bridging dithiolato ligand. Interactions of [Ru(PPh3)3Cl2] and [RuHCl(CO)(PPh3)3] with Lawesson’s reagent in the presence of ammonium hydroxide gave the dinuclear neutral complexes [Ru(μ-η1(O),η1(S),η1(S,S′)-ArPOS2)(PPh3)2]2 (2) and [Ru(CO)(μ-η1(O),η2(S,S′)-ArPOS2)(PPh3)]2 (3), respectively, in which the [ArPOS2]2− ligands bind the two Ru atoms via both sulfur and oxygen atoms. Reaction of dimeric [Cp*Ru(OMe)]2 (Cp* = η5-C5Me5) with Lawesson’s reagent in the presence of ammonium hydroxide led to isolation of a novel ruthenium(IV) complex, [Cp*Ru{(ArPS2O)2H}] (4). Reaction of [Ru(PPh3)3Cl2] or [RuHCl(CO)(PPh3)3] with Na[FcP(OMe)S2], which was prepared from [FcP(S)(μ-S)]2 (Fc = Fe(η5-C5H4)(η5-C5H5)) and MeONa in methanol, gave the neutral mononulcear complexes cis-[Ru{Fc(OCH3)PS2}2(L′)(PPh3)] (L′ = PPh3 5, CO 6). Interaction of [Ru(PPh3)3Cl2] or [RuHCl(CO)(PPh3)3] with [FcP(S)(μ-S)]2 in the presence of ammonium hydroxide in THF gave [Ru{Fc(OH)PS2}2(L′)(PPh3)] (L′ = PPh3 7, CO 8). Treatment of [(η6-p-cymene)RuCl(μ-Cl)]2 with [FcP(OH)S(SH)] in the presence of excess NaHCO3 led to isolation of [(η6-p-cymene)Ru{η1(S),η2(S,S′)-FcPS2OP(S)SFc}] (9). The crystal structures of 1, 2, 3·CH2Cl2·THF, 4·CH2Cl2·0.5H2O, 6, 7·CH2Cl2·3/4C6H14, and 9·CH2Cl2 along with their spectroscopic properties are reported.