Abstract

Photolysis of cis-(?5-C5Me5)Re(CO)2I 2 in the presence of P(OMe)3 led to the production of [(?5-C5Me5)Re(CO)2P(OMe) 3], MeI and OP(OMe)2I. The mechanism of the reaction has been studied both by low temperature and room temperature FTIR spectroscopy and by measurement of the quantum yields under conditions of varying P(OMe)3 concentration. The reaction occurs via initial loss of I- to generate the solvent caged ion pair [(?5-C5Me5)Re(CO)2I] +I-. This species then reacts with P(OMe)3 either within the solvent cage or following escape from the solvent cage, to form [(?5-C5Me5)Re (CO)2(THF)I]+. This complex then reacts with P(OMe)3 to generate the final products, [(?5-C5Me5)Re(CO)2P(OMe) 3], MeI and P(O)I(OMe)2. Copyright © 1996 Elsevier Science Ltd.