Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Academician Lavrentiev Avenue 3, Novosibirsk, 630090, Russian Federation.
J Comput Chem. 2013 Aug 15;34(22):1917-24. doi: 10.1002/jcc.23345. Epub 2013 Jun 7.
We report detailed study focused on the electron density redistribution during the simple oxidative addition reaction being the crucial stage of various catalytic processes. The bonding evolution theory based on the electron localization function and Thom's catastrophe theory shows that activation of methane's C-H bond by Pd atom consist of six elementary steps. The important feature revealed is the pronounced reorganization of Pd's outer core maxima corresponding to N-shell electrons of metal. Electronic rearrangements identified in this model reaction are likely to be the case in the more complex reactions of the same type involving transition metal compounds and, in principle, can be observed by modern ultrafast spectroscopy and diffraction techniques.
我们报告了一项详细的研究，重点关注简单氧化加成反应过程中电子密度再分配，这是各种催化过程的关键阶段。基于电子定域函数和 Thom 突变理论的成键演化理论表明，钯原子对甲烷 C-H 键的活化由六个基本步骤组成。揭示的重要特征是 Pd 外核最大值与金属 N 壳层电子的显著重排。在这个模型反应中确定的电子重排很可能是涉及过渡金属化合物的更复杂反应的情况，原则上可以通过现代超快光谱和衍射技术观察到。
