Abstract
UV irradiation of M(CO) 6 (M = Cr, Mo, W) in the presence of excess olefin yields light sensitie metal carbonylolefin complexes. Photoinduced rearrngement reactions of the olefin, including both cis-trans isomerization and 1,3-hydrogen shifts, take place. In addition, photosubstitution of both CO and the olefin occur in M(CO) n (olefin) 6 − n complexes with high quantum efficiency. Olefins investigted include the linear pentenes, linear hexenes, 1,4-pentadiene, 1,4-hexadienes, 1,3-pentadienes, 2,4-hexadienes, stilbenes, and trans-C 2H 2D 2. Photoassistance activity with respect to olefin isomerization depends on the metal in the order W > Mo > Cr. The evidence indicates that both photo and thermal pathways are of importance in olefin rearrangements of M(CO) n -(olefin) 6 − n .
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