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(sp)-H or C(sp)-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.

We have used dispersion-corrected DFT (DFT-D) together with solvation to examine possible mechanisms for reaction of PhX (X = Cl, Br, I) with Pd(P(t)Bu(3))(2) and compare our results to recently published kinetic data (F. Barrios-Landeros, B. P. Carrow and J. F. Hartwig, J. Am. Chem. Soc., 2009, 131, 8141-8154). The calculated activation free energies agree near-quantitatively with experimentally observed rate constants.

A seven‐membered N,N′‐heterocyclic potassium alumanyl nucleophile is introduced and utilised in the metathetical synthesis of Mg−Al and Ca−Al bonded derivatives. Both species have been characterised by experimental and theoretical means, allowing a rationalisation of the greater reactivity of the heavier group 2 species implied by an initial assay of their reactivity.

Kinetic analysis of the reaction of the copper(I) β-diketiminate [Cl(2)NN]Cu ([Cu(I)]) with (t)BuOO(t)Bu to give [Cu(II)]-O(t)Bu (1) reveals first-order behavior in each component implicating the formation of free (t)BuO(•) radicals. Added pyridine mildly inhibits this reaction indicating competition between (t)BuOO(t)Bu and py for coordination at [Cu(I)] prior to peroxide activation. Reaction of [Cu(I)] with dicumyl peroxide leads to [Cu(II)]-OCMe(2)Ph (3) and acetophenone suggesting the intermediacy of the PhMe(2)CO(•) radical. Computational methods provide insight into the activation of (t)BuOO(t)Bu at [Cu(I)]. The novel peroxide adduct [Cu(I)]((t)BuOO(t)Bu) (4) and the square planar [Cu(III)](O(t)Bu)(2) (5) were identified, each unstable toward loss of the (t)BuO(•) radical. Facile generation of the (t)BuO(•) radical is harnessed in the catalytic C-H etherification of cyclohexane with (t)BuOO(t)Bu at rt employing [Cu(I)] (5 mol %) to give the ether Cy-O(t)Bu in 60% yield.

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