Ghosh Bijoy, Phukan Ashwini K
Department of Chemical Sciences, Tezpur University, Napaam 784028, Assam, India.
Dalton Trans. 2020 Jul 17;49(27):9505-9515. doi: 10.1039/d0dt01363c.
Density functional theory calculations are employed to explore the reactivity of metalla-N-heterocyclic carbenes (MNHCs) towards activation of a variety of small molecules (H2, NH3, PH3, SiH3Ph and CH4). All the MNHCs considered are found to have a stable singlet ground state and possess suitable electronic properties for their application in small molecule activation. The calculated energy barriers of E-H (E = H, C, N, Si, P) activation for the MNHCs are found to be in agreement with those of the experimentally evaluated cyclic alkyl(amino)carbene (CAAC) and diamidocarbenes (DACs), thereby indicating the activating effect of the incorporation of an ancillary metal center within a cyclic NHC, and highlighting a new, underexplored strategy in achieving difficult bond activations with carbenes.
采用密度泛函理论计算来探究金属氮杂环卡宾（MNHCs）对各种小分子（H₂、NH₃、PH₃、SiH₃Ph和CH₄）的活化反应活性。所考虑的所有MNHCs均具有稳定的单重态基态，并且具备适合于在小分子活化中应用的电子性质。发现MNHCs对E-H（E = H、C、N、Si、P）活化的计算能垒与实验评估的环烷基（氨基）卡宾（CAAC）和二酰胺基卡宾（DACs）的能垒一致，从而表明在环状氮杂环卡宾中引入辅助金属中心的活化作用，并突出了一种利用卡宾实现困难键活化的新的、未充分探索的策略。
