Ruthenium Porphyrin Complexes Containing Thiocarbonyl or Cyanide Ligand
Smith, P.D., David Dolphin, and James, B.R.
J. Organomet. Chem.
Treatment of RuII(OEP)CO(py) (H2OEP = octaethylporphine) with Br2 in the presence of excess cyanide leads to oxidative decarbonylation and the formation of the isolable anion [RuIII(OEP)(CN)2]-, from which the neutral complex RuIII(OEP)CN(py) is readily obtained. Reduction of the neutral (cyano)pyridine species in the presence of thiophosgene leads to the formation of RuII(OEP)CS(py). The spectroscopic and electrochemical properties of the carbonyl and thiocarbonyl compounds within the series M(OEP)CX(Py) (M = Fe, Ru, Os; X = O, S) were examined and compared. The anionic species [Ru(OEP)CN(L)]- (L = CO, py) were also identified in solution.