title: Reduction of carbon monoxide by [(TMTAA)Rh]2 to form a dimetal ketone complex.
abstract: 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; ν(CO) = 1726 cm(-1); (1)J(103)Rh(13)C(O)(103)Rh = 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) × 10(3), ΔG(1)°(298 K) = -5.0(0.1) kcal mol(-1), ΔH(1)° = -14(1) kcal mol(-1), and ΔS(1)° = -30(3) cal K(-1) mol(-1)].
authors.affiliation: Department of Chemistry, Temple University, 130 Beury Hall, 1901 N. 13th Street, Philadelphia, Pennsylvania 19122, USA.
authors.forename: Gregory H
authors.initials: GH
authors.lastname: Imler
authors.forename: Salome
authors.initials: S
authors.lastname: Bhagan
authors.forename: Virginia L
authors.initials: VL
authors.lastname: Coffin
authors.forename: Bradford B
authors.initials: BB
authors.lastname: Wayland
mesh_terms: D002248:Carbon Monoxide / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D012211:Rhenium / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D007659:Ketones; D012211:Rhenium; D002248:Carbon Monoxide