Coordination-induced bond weakening is a phenomenon wherein ligand X–H bond homolysis occurs in concert with the energetically favorable oxidation of a coordinating metal complex. The coupling of these two processes enables thermodynamically favorable proton-coupled electron transfer reductions to form weak bonds upon formal hydrogen atom transfer to substrates. Moreover, systems utilizing coordination-induced bond weakening have been shown to facilitate the dehydrogenation of feedstock molecules including water, ammonia, and primary alcohols under mild conditions. The formation of exceptionally weak substrate X–H bonds via small molecule homolysis is a powerful strategy in synthesis and has been shown to enable nitrogen fixation under mild conditions. Coordination-induced bond weakening has also been identified as an integral process in biophotosynthesis and has promising applications in renewable chemical fuel storage systems. This review presents a discussion of the advances made in the study of coordination-induced bond weakening to date. Because of the broad range of metal and ligand species implicated in coordination-induced bond weakening, each literature report is discussed individually and ordered by the identity of the low-valent metal. We then offer mechanistic insights into the basis of coordination-induced bond weakening and conclude with a discussion of opportunities for further research into the development and applications of coordination-induced bond weakening systems.

中文翻译：

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配位诱导的债券弱化

配位诱导的键弱化是一种现象，其中配体 X-H 键均裂与配位金属配合物的能量有利氧化相一致。这两个过程的耦合使得热力学上有利的质子耦合电子转移还原能够在正式的氢原子转移到基板时形成弱键。此外，利用配位诱导键弱化的系统已被证明可以在温和条件下促进包括水、氨和伯醇在内的原料分子的脱氢。通过小分子均裂形成异常弱的底物 X-H 键是一种强大的合成策略，并且已被证明能够在温和条件下固氮。配位诱导的键弱化也被认为是生物光合作用的一个完整过程，并在可再生化学燃料储存系统中具有广阔的应用前景。本综述讨论了迄今为止在配位引起的键弱化研究中取得的进展。由于涉及配位诱导的键弱化的金属和配体种类繁多，因此每个文献报告都单独讨论并按低价金属的特性排序。然后，我们提供了对配位诱导的键弱化基础的机理见解，并讨论了进一步研究配位诱导的键弱化系统的开发和应用的机会。本综述讨论了迄今为止在配位引起的键弱化研究中取得的进展。由于涉及配位诱导的键弱化的金属和配体种类繁多，因此每个文献报告都单独讨论并按低价金属的特性排序。然后，我们提供了对配位诱导的键弱化基础的机理见解，并讨论了进一步研究配位诱导的键弱化系统的开发和应用的机会。本综述讨论了迄今为止在配位引起的键弱化研究中取得的进展。由于涉及配位诱导的键弱化的金属和配体种类繁多，因此每个文献报告都单独讨论并按低价金属的特性排序。然后，我们提供了对配位诱导的键弱化基础的机理见解，并讨论了进一步研究配位诱导的键弱化系统的开发和应用的机会。每个文献报告都单独讨论，并按低价金属的特性排序。然后，我们提供了对配位诱导的键弱化基础的机理见解，并讨论了进一步研究配位诱导的键弱化系统的开发和应用的机会。每个文献报告都单独讨论，并按低价金属的特性排序。然后，我们提供了对配位诱导的键弱化基础的机理见解，并讨论了进一步研究配位诱导的键弱化系统的开发和应用的机会。