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

Treatment of dimeric [(η 6 - p -cymene)RuCl(μ-Cl)] 2 with Lawesson’s reagent [ArP(S)(μ-S)] 2 (Ar = p -C 6 H 4 OMe) in THF gave [(η 6 - p -cymene)Ru{μ-η 1 ( S ),η 2 ( S, S ′)-ArP(S)S 2 }] 2 ( 1 ) as the sole isolable product. The chlorides in the starting ruthenium compound were substituted by [ArP(S)S 2 ] 2− as a bridging dithiolato ligand. Interactions of [Ru(PPh 3 ) 3 Cl 2 ] and [RuHCl(CO)(PPh 3 ) 3 ] with Lawesson’s reagent in the presence of ammonium hydroxide gave the dinuclear neutral complexes [Ru(μ-η 1 ( O ),η 1 ( S ),η 1 ( S, S ′)-ArPOS 2 )(PPh 3 ) 2 ] 2 ( 2 ) and [Ru(CO)(μ-η 1 ( O ),η 2 ( S, S ′)-ArPOS 2 )(PPh 3 )] 2 ( 3 ), respectively, in which the [ArPOS 2 ] 2− ligands bind the two Ru atoms via both sulfur and oxygen atoms. Reaction of dimeric [Cp*Ru(OMe)] 2 (Cp* = η 5 -C 5 Me 5 ) with Lawesson’s reagent in the presence of ammonium hydroxide led to isolation of a novel ruthenium(IV) complex, [Cp*Ru{(ArPS 2 O) 2 H}] ( 4 ). Reaction of [Ru(PPh 3 ) 3 Cl 2 ] or [RuHCl(CO)(PPh 3 ) 3 ] with Na[FcP(OMe)S 2 ], which was prepared from [FcP(S)(μ-S)] 2 (Fc = Fe(η 5 -C 5 H 4 )(η 5 -C 5 H 5 )) and MeONa in methanol, gave the neutral mononulcear complexes cis -[Ru{Fc(OCH 3 )PS 2 } 2 (L′)(PPh 3 )] (L′ = PPh 3 5, CO 6 ). Interaction of [Ru(PPh 3 ) 3 Cl 2 ] or [RuHCl(CO)(PPh 3 ) 3 ] with [FcP(S)(μ-S)] 2 in the presence of ammonium hydroxide in THF gave [Ru{Fc(OH)PS 2 } 2 (L′)(PPh 3 )] (L′ = PPh 3 7, CO 8 ). Treatment of [(η 6 - p -cymene)RuCl(μ-Cl)] 2 with [FcP(OH)S(SH)] in the presence of excess NaHCO 3 led to isolation of [(η 6 - p -cymene)Ru{η 1 ( S ),η 2 ( S, S ′)-FcPS 2 OP(S)SFc}] ( 9 ). The crystal structures of 1, 2, 3 ·CH 2 Cl 2 ·THF, 4 ·CH 2 Cl 2 ·0.5H 2 O, 6, 7 ·CH 2 Cl 2 · 3 / 4 C 6 H 14, and 9 ·CH 2 Cl 2 along with their spectroscopic properties are reported.