Dinitrogen Splitting Coupled to Protonation.
Dinitrogen Splitting Coupled to Protonation.
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DOI：
10.1002/anie.201701504
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发表时间：
2017-05
影响因子：
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通讯作者：
G. A. Silantyev;M. Förster;Bastian Schluschaß;Josh Abbenseth;Christian Würtele;Christian Volkmann;M. C. Holthausen;S. Schneider
中科院分区：
文献类型：
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作者：
G. A. Silantyev;M. Förster;Bastian Schluschaß;Josh Abbenseth;Christian Würtele;Christian Volkmann;M. C. Holthausen;S. Schneider
电子和质子转移步骤的耦合为控制氧化还原反应的驱动力提供了一个普遍的概念。本文报道了氮气分解钼氮氮络合物生成氮化物的反应。值得注意的是，我们的光谱、动力学和计算机制分析将N-N键断裂归因于酰胺钳形配体外围的质子化，而不是{Mo-N-Mo}核心。N-N键断裂对电子结构以及最终的热化学和动力学势垒的强烈影响是质子耦合的金属到配体电荷转移过程的罕见情况，突出了质子响应配体用于固氮的使用。
The coupling of electron- and proton-transfer steps provides a general concept to control the driving force of redox reactions. N2 splitting of a molybdenum dinitrogen complex into nitrides coupled to a reaction with Brønsted acid is reported. Remarkably, our spectroscopic, kinetic, and computational mechanistic analysis attributes N-N bond cleavage to protonation in the periphery of an amide pincer ligands rather than the {Mo-N2 -Mo} core. The strong effect on electronic structure and ultimately the thermochemistry and kinetic barrier of N-N bond cleavage is an unusual case of a proton-coupled metal-to-ligand charge transfer process, highlighting the use of proton-responsive ligands for nitrogen fixation.