The Photochemistry of Metal Carbonyls

Many of the qualitative aspects of metal carbonyl photochemistry are known, and in particular a rather dramatic increase in lability in the M-CO bond seems virtually universal upon photoexcitation. Photolysis of the substituted derivatives of the binary compounds often results in alternate deactivation pathways at least as some fraction of the chemical action. Despite the collosal number of known metal carbonyls and their derivatives (many synthesized with light), there is a rather disappointing amount of sophistication regarding structure-reactivity relationships. The reviewer feels that several areas merit focused attention. First, information concerning the nature of the electronic states available at optical energies should be pursued. Identification of the reactive excited states and their conversion pathways to other electronic states is of interest. Developing geometrical and electronic structure-reactivity relationships is of importance. And, finally, as chemists, our knowledge concerning primary processes in metal carbonyls should be directed toward generation of catalytically active species and synthetically useful molecules. Acknowledgment. The research carried out in the reviewer's laboratory cited in the references was supported by the National Science Foundation.