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.