Copper–Nitrene Complexes in Catalytic CH Amination

Activation of Carbon−Hydrogen and Hydrogen−Hydrogen Bonds by Copper−Nitrenes: A Comparison of Density Functional Theory with Single- and Multireference Correlation Consistent Composite Approaches

“…Previous DFT calculations in concert with experimental studies support a mechanism involving direct [1 + 2] insertion. 30 On the singlet surface for H 2 functionalization, the [1 + 2] insertion reaction is calculated to be exothermic by -72.5 kcal mol -1 versus -83.9 kcal mol -1 determined at the B3LYP/6-311++G(d,p) level of theory, Table 1. The singlet insertion barrier is small using both density functional and wave function based techniques (3.4 kcal mol -1 for B3LYP/6-311++G(d,p) and 5.9 kcal mol -1 for ccCA).…”

A potential role of a substrate as a base for the deprotonation pathway in Rh-catalysed C–H amination of heteroarenes: DFT insights

“…In fact, metal-nitrenoid species are known to be generated in such reactions and a few examples of C-N bond formation upon treatment of the corresponding metal-nitrenoid species with hydrocarbons have also been reported. [25][26][27][28][29] The Scheme 2. Possible mechanism of C-H amination using phenyl azide as the nitrogen source.…”

C–H Functionalization Reactivity of a Nickel–Imide

“…8,11,19,26 Cundari and co-workers described computational studies of Fe to Cu nitrene complexes featuring chelating phosphines and β-diketiminate supporting ligands. 27,28 In particular, the thermodynamic favorability of methane C−H amination to give β-diketiminato [M](NH-(Me)R) products increases dramatically as the metal is changed from Fe to Cu in an analogous series of neutral [M]NR complexes.…”

“…11 The β-diketiminato copper(I) complex {[Cl 2 NN]Cu} 2 (μ-benzene) also catalytically aminates C−H bonds in hydrocarbons (R−H) to give amines (HN(R)Ad) in high yields using N 3 Ad as the nitrene transfer reagent (Scheme 2). 11,29 In light of the efficient stoichiometric and catalytic C−H amination by its copper analogue and the aforementioned computational studies of nickel complexes, we reinvestigated the reactivity of [Me 3 NN]NiNAd (1) with benzylic C−H substrates. Specifically, we were interested in the potential to couple previously observed HAA and C−N bond forming reactions (Scheme 1) in a complete C−H functionalization sequence employing a single substrate R−H to give the new amine R−NHAd.…”