Photooxidation of Rh(PPh3)(2)(CS)Cl induced by metal-to-ligand charge transfer excitation

The longest-wavelength absorption of Rh-I(PPh3)(2)(CS)Cl at lambda(max) = 4 52 nm is assigned to a metal-to-ligand charge transfer (MLCT) transition wh ich terminates at the pi* orbital of the thiocarbonyl ligand. MLCT excitati on of the complex in CH2Cl2 initiates a photooxidation which finally leads to Rh-III(PPh3)(2)(CS)Cl-3 as a stable photoproduct with phi = 0.003 at lam bda(irr) = 436 nm. (C) 1999 Elsevier Science S.A. All rights reserved.