Reactions of CO2 and CS2 with [RuH(η2‑CH2PMe2)(PMe3)3]
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Carbon disulfide reacted with the cyclometalated ruthenium complex [RuH(η2-CH2PMe2)(PMe3)3] (1) at low temperature to yield the dithioformate complex [Ru(η1-SC(S)H)(η2-CH2PMe2)(PMe3)3] (4), where the CS2 inserts into the metal hydride bond. On warming, complex 4 rearranges to give the known complex [Ru(S2CHPMe2CH2-κ3S,S,C)(PMe3)3] (3), where the CS2 is inserted in a metal phosphorus bond. Further reaction of this complex with excess CS2 over a period of days resulted in insertion of a second CS2 unit into one Ru–S bond to yield [Ru(SC(S)SCH(-S)PMe2CH2-κ3S,S,C)(PMe3)3] (5). Complex 5 was characterized crystallographically and by multinuclear NMR spectroscopy. In contrast, reaction of [RuH(η2-CH2PMe2)(PMe3)3] (1) with CO2 resulted in insertion of CO2 into the Ru–C bond to give [RuH(OC(O)CH2PMe2-κ2O,P)(PMe3)3] (2). Low-temperature NMR spectroscopic studies did not show any evidence for prior formation of a formate complex.
