Photooxidation of Rh(PPh 3) 2(CS)Cl induced by metal-to-ligand charge transfer excitation

Abstract

The longest-wavelength absorption of Rh I(PPh 3) 2(CS)Cl at λ max=452 nm is assigned to a metal-to-ligand charge transfer (MLCT) transition which terminates at the π* orbital of the thiocarbonyl ligand. MLCT excitation of the complex in CH 2Cl 2 initiates a photooxidation which finally leads to Rh III(PPh 3) 2(CS)Cl 3 as a stable photoproduct with φ=0.003 at λ irr=436 nm.