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The multiphoton photochemistries of a variety of gas phase transition metal carbonylcomplexes are investigated by MPI time-of-flight mass spectrometry, and resultsindicate that molecular fragment ionization can compete with atomization in thesesystems. Molecular ions detected include a variety of homonuclear and heteronuclearbare metal clusters, metal-sulfur clusters and metal monocarbonyls. Thus, multiphotonexcitation of stable metal carbonyl compounds provides a versatile synthetic route tohighly unsaturated neutral and ionic gas phase clusters which offers unique productcluster specificity and does not require the use of high temperature sources. Thedetection under collision-free conditions of bare metal dimers and trimers followingMPI of several dinuclear and trinuclear metal cluster carbonyl compounds, respectively,indicates that dissociative CO loss can compete with metal–metal bond cleavage as aprimary excited state reaction upon UV photolysis of these systems.

Multiphoton Ionization Mass Spectrometric Studies of Transition Metal Carbonyl Complexes