Abstract
The past several decades have witnessed enormous growth in what we know about the synthesis, reactivity, reaction mechanisms, molecular structures, and electronic structures of organometallic molecules. Curiously, however, we know far less about the thermodynamics of most organometallic transformations and, in particular, about the exact strengths of metal-ligand bonds. In principle, such information offers a better understanding of metal-ligand bonding, a better insight into the course(s) of known reactions, and a valuable advantage in designing new transformations.1–5 For organometallic chemistry involving actinides, lanthanides, and early transition elements, our thermochemical/calorimetric investigations were motivated by growing evidence that deviations in reactivity patterns from those of middle and late transition elements could not be explained by kinetic factors alone. In the present chapter, we briefly review some of our recent results in this area, focusing upon how ancillary ligands affect metal-ligand bond enthalpies, metal-ligand bonding patterns as a function of position in the Periodic Table, and the thermochemically-assisted design of a new catalytic reaction pattern: organolanthanide-catalyzed hydroamination.
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Gagne, M.R., Nolan, S.P., Seyam, A.M., Stern, D., Marks, T.J. (1990). Thermochemical Aspects of Organotransition Metal Chemistry. Insights Provided by Metal-Ligand Bond Enthalpies. In: Fackler, J.P. (eds) Metal-Metal Bonds and Clusters in Chemistry and Catalysis. Industry-University Cooperative Chemistry Program Symposia. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-2492-6_9
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