Computational Studies of Carboxylate-Assisted C–H Activation and Functionalization at Group 8–10 Transition Metal Centers

Computational studies on carboxylate-assisted C–H activation and functionalization at group 8–10 transition metal centers are reviewed. This Review is organized by metal and will cover work published from late 2009 until mid-2016. A brief overview of computational work prior to 2010 is also provided, and this outlines the understanding of carboxylate-assisted C–H activation in terms of the “ambiphilic metal–ligand assistance” (AMLA) and “concerted metalation deprotonation” (CMD) concepts. Computational studies are then surveyed in terms of the nature of the C–H bond being activated (C(sp2)–H or C(sp3)–H), the nature of the process involved (intramolecular with a directing group or intermolecular), and the context (stoichiometric C–H activation or within a variety of catalytic processes). This Review aims to emphasize the connection between computation and experiment and to highlight the contribution of computational chemistry to our understanding of catalytic C–H functionalization based on carboxylate-assisted C–H activation. Some opportunities where the interplay between computation and experiment may contribute further to the areas of catalytic C–H functionalization and applied computational chemistry are identified.