Abstract
A self-consistent field analysis of the photolysis of [Mn(CO)5Cl] has been performed. Based on electron-density difference plots and population analysis a correlation is made between the nature of the photoactive state and the preferential leaving ligand. The stereochemistry of the photolysis reaction has been determined by a study of the possible excited-state isomerization pathways of the five-co-ordinated structure [Mn(CO)4Cl]. The analysis confirms the experimentally observed trans→cis stereopreference.
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