Organometallic photochemistry: AB initio potential energy surfaces as reaction maps of the primary photoprocess

Abstract

The mechanism of the primary photoprocess for several photochemical reactions of organomettalic molecules will be discussed on the basis of ab initio potential energy curves obtained from Contracted Configuration Interaction calculations based on Complete Active Space SCF wavefunctions. The photoactive excited states responsible for the photoelimination of molecular hydrogen in H 2Fe(CO) 4, the loss of a carbonyl ligand and the homolysis of the metal-hydrogen bond in HMn(CO) 5 will be specified as well as the corresponding reaction paths. The mechanism of the double photochemistry of HMn(CO) 5 will be compared to the photoreactivity of HCo(CO) 4.