Mechanistic Study for the Photochemical Reactions of d⁶ M(CO)₅(CS) (M = Cr, Mo, and W) Complexes.

ABSTRACT: The mechanisms of photoextrusion reactions are determined theoretically for the model system of six-coordinated M(CO)₅(CS) (M = Cr, Mo, and W), using both CASSCF and MP2-CAS methods and the Def2-SVPD basis set. Three types of elimination reaction pathways (i.e., path I, path II, and path III for axial CO extrusion, equatorial CO extrusion, and CS ligand extrusion, respectively) are considered in this study. Theoretical findings show that the photoextrusion mechanism for Cr and Mo complexes proceeds as follows: M-S₀-Rea + hν → M-S₁-FC → M-CI → M-Pro + CO. This study shows that when the reactant, M(CO)₅(CS) (M-S₀-Rea), is photoirradiated by UV light, it is excited vertically to many low-lying singlet excited states. It then relaxe

SUBMITTER: Zhang ZF 

PROVIDER: S-EPMC6641059 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature