PHOTOREACTIVITY OF FE2S2(CO)(6) ORIGINATING FROM D-SIGMA-ASTERISK METAL-TO-LIGAND CHARGE-TRANSFER EXCITATION

The longest-wavelength absorption of Fe2S2(CO)(6), near 460 nm is assi gned to a metal-to-ligand charge transfer (MLCT) transition from the F e-Fe bond to a S-S antibonding orbital. It is suggested that MLCT exci tation leads to an oxidative addition. The primary photoproduct reacts with Fe2S2(CO)(6) to generate Fe4S4(CO)(12). This well known photodim erization proceeds with phi = 0.045 at lambda(irr) = 436 nm. (C) 1998 Elsevier Science S.A. All rights reserved.