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Organolanthanide mediated catalytic cycles: a computational perspective.

In this perspective the contribution of recent theoretical studies to our understanding of lanthanide (Ln) catalysis is explored. In general, the results of computational studies have proven consistent with available experimental evidence. Considerable success has been obtained in elucidating the mechanisms for C-H bond activation (sigma-bond metathesis in particular) and the addition of C-X bonds across an unsaturated functionality (and the hydroamination of alkenes in particular). Ln catalysts are computationally challenging because relativistic effects are important, and large ligands are required to restrict high coordination numbers, in addition to limiting facile redistribution processes. Thus, key technical issues relating to the computational investigation of organolanthanide complexes are discussed. Increasing computational resources have seen studies expand from the optimisation of simple molecules to the study of catalytic cycles where the Ln is coordinated by larger and more complex ligands. The ability of theoretical studies to complement experimental developments by supplying a deeper understanding of the mechanistic process is reviewed with emphasis on the elucidation of transition state structures, intermediates, spectator ligand coordination, and negative entropy steps. Recent computational investigations of the catalytic cycle for Ln mediated hydroamination are a focus, as these have provided substantial and detailed rationalisations for the regio- and stereo-selectivity of inter- and intra-molecular hydroamination. Examination of transition state geometries and electronic structure appears to offer insights that could be used to facilitate the rational design of new Ln-based catalysts.