Roux Yoann, Duboc Carole, Gennari Marcello
Département de Chimie Moléculaire (UMR 5250), Univ. Grenoble Alpes, CNRS, F-38000, Grenoble, France.
Chemphyschem. 2017 Oct 6;18(19):2606-2617. doi: 10.1002/cphc.201700665. Epub 2017 Sep 27.
Fixation of atmospheric nitrogen is central for the production of ammonia, which is the source of nitrogen fertilizers and is also emerging as a promising renewable fuel. While the development of efficient molecular-based artificial nitrogen fixation systems working under mild conditions is probably a Holy Grail, the catalytic reduction of N by transition-metal complexes is-above all-the main instrument to progress in the mechanistic understanding of N splitting. In this Minireview we first give an overview of molecular-based catalytic systems, including recent breakthroughs, and then we illustrate the alternative pathways for N reduction. We mainly focus on multistep hydrogenation of N by separated proton and electron sources, with a particular attention for the possibility of proton-coupled electron transfer events. Finally, we try to identify the key factors to achieve catalytic reduction of dinitrogen by metal complexes and to enhance their efficiency.
大气氮的固定对于氨的生产至关重要，氨是氮肥的来源，同时也正成为一种有前景的可再生燃料。虽然开发在温和条件下工作的高效分子基人工固氮系统可能是一个圣杯，但过渡金属配合物催化还原N首先是在N分裂机理理解方面取得进展的主要手段。在这篇综述中，我们首先概述了分子基催化系统，包括最近的突破，然后阐述了N还原的替代途径。我们主要关注通过分离的质子和电子源对N进行多步氢化，特别关注质子耦合电子转移事件的可能性。最后，我们试图确定实现金属配合物催化还原二氮并提高其效率的关键因素。
