Department of Chemistry, ‡Center for Computational Chemistry, and §College of Engineering, University of Georgia , Athens, Georgia 30602, United States.
J Org Chem. 2014 Feb 21;79(4):1836-41. doi: 10.1021/jo402259z. Epub 2014 Feb 10.
The kinetic isotope effect (KIE) is used to experimentally elucidate the first irreversible step in oxidative addition reactions of a zerovalent nickel catalyst to a set of haloarene substrates. Halogenated o-methylbenzene, dimethoxybenzene, and thiophene derivatives undergo intramolecular oxidative addition through irreversible π-complexation. Density functional theory computations at the B3LYP-D3/TZ2P-LANL2TZ(f)-LANL08d level predict η(2)-bound π-complexes are generally stable relative to a solvated catalyst plus free substrate and that ring-walking of the Ni(0) catalyst and intramolecular oxidative addition are facile in these intermediates.
动力学同位素效应（KIE）用于实验阐明零价镍催化剂与一系列卤代芳烃底物的氧化加成反应中的第一个不可逆步骤。卤代邻甲基苯、二甲氧基苯和噻吩衍生物通过不可逆的π-络合作用进行分子内氧化加成。在 B3LYP-D3/TZ2P-LANL2TZ(f)-LANL08d 水平下的密度泛函理论计算预测，相对于溶剂化催化剂加游离底物，η(2)-键合的π-络合物通常是稳定的，并且 Ni(0)催化剂的环行走和分子内氧化加成在这些中间体中是容易进行的。
