om3011307_si_001.cif (49.36 kB)

Reactions of CO2 and CS2 with [RuH(η2‑CH2PMe2)(PMe3)3]

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posted on 28.01.2013, 00:00 by Leslie D. Field, Peter M. Jurd, Alison M. Magill, Mohan M. Bhadbhade
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(S2CHPMe2CH23S,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)­PMe2CH23S,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)­CH2PMe22O,P)­(PMe3)3] (2). Low-temperature NMR spectroscopic studies did not show any evidence for prior formation of a formate complex.