The mechanistic investigations of photochemical decarbonylations and oxidative addition reactions for M(CO)₅ (M = Fe, Ru, Os) complexes.

ABSTRACT: The mechanisms for the photochemical CO-dissociation and the oxidative addition reactions are studied theoretically using three model systems: M(CO)₅ (M = Fe, Ru, and Os) and the CASSCF/Def2-SVP (fourteen-electron/ten-orbital active space) and MP2-CAS/Def2-SVP//CASSCF/Def2-SVP methods. The structures of the intersystem crossings and the conical intersections, which play a decisive role in these CO photo-extrusion reactions, are determined. The intermediates and the transition structures in either the singlet or triplet states are also computed, in order to explain the reaction routes. These model studies suggest that after the irradiation of Fe(CO)₅ with UV light, it quickly loses one CO molecule to generate a 16-electron iron tetracarbonyl, in either the singlet or t

SUBMITTER: Zhang ZF 

PROVIDER: S-EPMC9059829 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature