The mechanistic investigations of photochemical carbonyl elimination and oxidative addition reactions of (η5-C5H5)M(CO)3, (M = Mn and Re) complexes

Abstract

We used computational methods to explore the mechanisms of the photochemical decarbonylation and the Si-H bond activation reaction of the group 7 organometallic compounds, η5-CpM(CO)3 (M = Mn and Re). The energies of both conical intersections and the intersystem crossings, which play a decisive role in these photo-activation reactions, are determined. Both intermediates and transition states in either the singlet or triplet states are also computed to furnish a mechanistic interpretation of the whole reaction paths. In the case of Mn, four types of reaction pathways (path I-path IV) that lead to the final insertion product are examined. The theoretical findings suggest that at the higher-energy band (295 nm) the singlet-state channel is predominant. As a result, the conical intersection mechanism (i.e., path I) prevails. However, at the lower-energy band (325 nm) the triplet-state channel occurs. In such a situation, the intersystem crossing mechanism (i.e., path IV) can successfully explain its CO-photodissociation mechanism. In the case of Re, on the other hand, the theoretical evidence reveals that only the singlet state-channel is superior. In consequence, the conical intersection mechanism (i.e., path V) can more effectively explain its photochemical decarbonylation mechanism. These theoretical analyses agree well with the available experimental observations.