Inorganic Chemistry, Vol.51, No.6, 3352-3354, 2012
Reduction of Carbon Monoxide by [(TMTAA)Rh](2) To Form a Dimetal Ketone Complex
Benzene solutions of [(TMTAA)Rh](2) (1) react with CO (P-CO = 0.8-20 atm; T = 298 K) by cleaving the Rh-II-Rh-II bond to form dirhodium(III) ketone (TMTAA)Rh-C (O)-Rh(TMTAA) [2; v(CO) = 1726 cm(-1); (I)J(103)Rh(13)C(O)Rh-103 = 45 Hz]. Thermodynamic values for the reaction of 1 with CO to form 2 were evaluated from equilibrium constant measurements [K-1(298 K) = 5.0(0.6) x 10(3), Delta G(1)degrees(298 = -5.0(0.1) kcal mol(-1), Delta H-1 degrees = -14(1) kcal mol(-1), and Delta S-1 degrees = -30(3) cal K-1 mol(-1)].