Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
Chem Rev. 2020 Jun 24;120(12):5582-5636. doi: 10.1021/acs.chemrev.9b00638. Epub 2020 Apr 30.
Nitrogen fixation, the six-electron/six-proton reduction of N, to give NH, is one of the most challenging and important chemical transformations. Notwithstanding the barriers associated with this reaction, significant progress has been made in developing molecular complexes that reduce N into its bioavailable form, NH. This progress is driven by the dual aims of better understanding biological nitrogenases and improving upon industrial nitrogen fixation. In this review, we highlight both mechanistic understanding of nitrogen fixation that has been developed, as well as advances in yields, efficiencies, and rates that make molecular alternatives to nitrogen fixation increasingly appealing. We begin with a historical discussion of N functionalization chemistry that traverses a timeline of events leading up to the discovery of the first molecular catalyst system and follow with a comprehensive overview of d-block compounds that have been targeted as catalysts up to and including 2019. We end with a summary of lessons learned from this significant research effort and last offer a discussion of key remaining challenges in the field.
固氮作用，即将 N 分子中的六个电子和六个质子还原成 NH，是最具挑战性和重要的化学转化之一。尽管该反应存在相关障碍，但在开发能够将 N 还原为其生物可用形式 NH 的分子配合物方面已经取得了重大进展。这一进展的驱动力来自于更好地理解生物固氮酶和改进工业固氮的双重目标。在这篇综述中，我们强调了固氮作用的机制理解的发展，以及在产率、效率和速率方面的进展，这些进展使得固氮的分子替代方法越来越有吸引力。我们从 N 官能化化学的历史讨论开始，该讨论跨越了导致发现第一个分子催化剂系统的一系列事件的时间线，然后全面概述了截至 2019 年被视为催化剂的 d 区化合物。最后，我们总结了从这项重要研究工作中吸取的经验教训，并最后讨论了该领域关键的遗留挑战。
