Multiphoton Ionization Mass Spectrometric Studies of Transition Metal Carbonyl Complexes

Abstract

The multiphoton photochemistries of a variety of gas phase transition metal carbonyl complexes are investigated by MPI time‐of‐flight mass spectrometry, and results indicate that molecular fragment ionization can compete with atomization in these systems. Molecular ions detected include a variety of homonuclear and heteronuclear bare metal clusters, metal‐sulfur clusters and metal monocarbonyls. Thus, multiphoton excitation of stable metal carbonyl compounds provides a versatile synthetic route to highly unsaturated neutral and ionic gas phase clusters which offers unique product cluster specificity and does not require the use of high temperature sources. The detection under collision‐free conditions of bare metal dimers and trimers following MPI of several dinuclear and trinuclear metal cluster carbonyl compounds, respectively, indicates that dissociative CO loss can compete with metal–metal bond cleavage as a primary excited state reaction upon UV photolysis of these systems.