Generation of an (alkoxycarbonyl)rhodium complex in an alcohol analog of the water-gas shift reaction

Article abstract of DOI:10.1021/om00028a033

(Octaethylporphyrinato)rhodium(II) dimer ((OEPRh)₂, 1) reacts with CO and ethanol in CH₂Cl₂ to give (octaethylporphyrinato)rhodium(III) chloride (5), (ethoxycarbonyl)(octaethylporphyrinato)rhodium(III) (OEPRh(CO)OEt, 6), and formyl(octaethylporphyrinato)rhodium(III) (2). The structure of 6 was clarified by X-ray diffraction analysis. Complex 6 crystallized in the monoclinic space group P2₁/n (No. 14) with a = 14.581 (1) ?, b = 14.181 (2) ?, c = 17.4530 (9) ?, V = 3608.8 (9) ?³, Z = 4, R = 0.046, R_w = 0.051, and T = 293 K for 415 parameters and 4864 reflections. The ¹H and ¹³C spectral properties of 2 and 6 in CD₂Cl₂ were determined and the behaviors of 1, 2, (octaethylporphyrinato)rhodium(III) hydride (3), and 6 in CH₂Cl₂ solvent were examined. Photolysis of 2 in CH₂Cl₂ at 300 nm afforded (octaethylporphyrinato)rhodium(III) chloride. Treatment of OEPCoNa with acetic anhydride in ethylene glycol dimethyl ether afforded acetyl(octaethylporphyrinato)cobalt(III) and an analogous experiment with acetic formic anhydride generated an acyl(octaethylporphyrinato)cobalt(III) complex.