文摘
Carbon disulfide reacted with the cyclometalated ruthenium complex [RuH(畏2-CH2PMe2)(PMe3)3] (1) at low temperature to yield the dithioformate complex [Ru(畏1-SC(鈺怱)H)(畏2-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-魏3S,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鈥揝 bond to yield [Ru(SC(鈺怱)SCH(-S)PMe2CH2-魏3S,S,C)(PMe3)3] (5). Complex 5 was characterized crystallographically and by multinuclear NMR spectroscopy. In contrast, reaction of [RuH(畏2-CH2PMe2)(PMe3)3] (1) with CO2 resulted in insertion of CO2 into the Ru鈥揅 bond to give [RuH(OC(鈺怬)CH2PMe2-魏2O,P)(PMe3)3] (2). Low-temperature NMR spectroscopic studies did not show any evidence for prior formation of a formate complex.
