The Electric Field as a “Smart” Ligand in Controlling the Thermal Activation of Methane and Molecular Hydrogen,Angewandte Chemie International Edition

当前位置： X-MOL 学术 › Angew. Chem. Int. Ed. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

The Electric Field as a “Smart” Ligand in Controlling the Thermal Activation of Methane and Molecular Hydrogen
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-07-13 , DOI: 10.1002/anie.201805718
Lei Yue ₁ , Na Wang ₁ , Shaodong Zhou _{1,

2} , Xiaoyan Sun ₁ , Maria Schlangen ₁ , Helmut Schwarz ₁

Affiliation

While pristine [TaO₂]⁺ is rather inert in its thermal reactions with both methane and molecular hydrogen, the cluster oxide becomes reactive upon ligation with the closed‐shell ligand CO₂. While the presence of CO₂ increases the intrinsic barriers of the C−H and H−H bond activation steps, the efficiency of the overall reaction to generate the insertion product [Ta(R)(OH)O]⁺ (R=CH₃, H) is greatly enhanced by the superb leaving‐group properties of CO₂. The ligand effect of CO₂ has been well mimicked by the electric field of a negative point charge, and mechanistic aspects are addressed by high‐level quantum chemical calculations

中文翻译：

电场作为控制甲烷和分子氢的热活化的“智能”配体

原始[TaO ₂ ] ⁺在与甲烷和分子氢的热反应中相对惰性，而簇状氧化物在与闭壳配体CO ₂连接后变得具有反应性。虽然CO ₂的存在增加了CH和H-H键活化步骤的内在壁垒，但产生插入产物[Ta（R）（OH）O] ⁺（R = CH ₃，H）通过出色的CO ₂离去基团性质大大增强了。负电荷的电场已很好地模拟了CO ₂的配体效应，并且通过高级量子化学计算解决了机械方面的问题。

更新日期：2018-07-13

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11