The eight very useful(η5 -C5R5)Re(CO)2L complexes, where R = H, CH3 and L = PMe3, PMe2Ph, PMePh2, PPh3, were prepared by the UV photolysis of (η5-C5R5)Re(CO)3 in THF solvent in the presence of the phosphine. The complexes were characterized by their v(CO) and 1H NMR spectra. © 1990, Taylor & Francis Group, LLC. All rights reserved.