Zhou Shaodong, Firouzbakht Marjan, Schlangen Maria, Kaupp Martin, Schwarz Helmut
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, P. R. China.
Chemistry. 2017 Oct 17;23(58):14430-14433. doi: 10.1002/chem.201703767. Epub 2017 Sep 18.
The gas-phase reactions of [NiL] (L=C H , C H N, CN) with methane have been explored by using electrospray-ionization mass spectrometry (ESI-MS) complemented by quantum chemical calculations. Though the phenyl Ni complex [Ni(C H )] exclusively abstracts one hydrogen atom from methane at ambient conditions, the cyano Ni complex [Ni(CN)] brings about both H-atom abstraction and ligand exchange to generate [Ni(CH )] . In contrast, the complex 2-pyridinyl Ni [Ni(C H N)] is inert towards this substrate. The presence of the empty 4s(Ni) orbital dominates the proton-coupled electron transfer (PCET) processes for the investigated systems.
通过电喷雾电离质谱（ESI-MS）并辅以量子化学计算，研究了[NiL]（L = C₆H₅、C₅H₅N、CN）与甲烷的气相反应。尽管苯基镍配合物[Ni(C₆H₅)]在环境条件下仅从甲烷中夺取一个氢原子，但氰基镍配合物[Ni(CN)]会导致氢原子夺取和配体交换，生成[Ni(CH₃)]⁺。相比之下，2-吡啶基镍配合物[Ni(C₅H₅N)]对该底物呈惰性。空的4s(Ni)轨道的存在主导了所研究体系的质子耦合电子转移（PCET）过程。
