Sinhababu Soumen, Singh Roushan Prakash, Radzhabov Maxim R, Kumawat Jugal, Ess Daniel H, Mankad Neal P
Department of Chemistry, University of Illinois Chicago, Chicago, IL, 60607, USA.
Department of Chemistry and Biochemistry, Brigham Young University, Provo, 84604, UT, USA.
Nat Commun. 2024 Feb 13;15(1):1315. doi: 10.1038/s41467-024-45721-1.
Several renewable energy schemes aim to use the chemical bonds in abundant molecules like water and ammonia as energy reservoirs. Because the O-H and N-H bonds are quite strong (>100 kcal/mol), it is necessary to identify substances that dramatically weaken these bonds to facilitate proton-coupled electron transfer processes required for energy conversion. Usually this is accomplished through coordination-induced bond weakening by redox-active metals. However, coordination-induced bond weakening is difficult with earth's most abundant metal, aluminum, because of its redox inertness under mild conditions. Here, we report a system that uses aluminum with a redox non-innocent ligand to achieve significant levels of coordination-induced bond weakening of O-H and N-H bonds. The multisite proton-coupled electron transfer manifold described here points to redox non-innocent ligands as a design element to open coordination-induced bond weakening chemistry to more elements in the periodic table.
几种可再生能源方案旨在利用水和氨等丰富分子中的化学键作为能量储存库。由于O-H键和N-H键相当强（>100千卡/摩尔），因此有必要识别能显著削弱这些键的物质，以促进能量转换所需的质子耦合电子转移过程。通常这是通过氧化还原活性金属的配位诱导键弱化来实现的。然而，由于铝在温和条件下的氧化还原惰性，对于地球上含量最丰富的金属铝来说，配位诱导键弱化是困难的。在此，我们报道了一个系统，该系统使用铝与氧化还原非无辜配体，以实现O-H键和N-H键显著程度的配位诱导键弱化。这里描述的多位点质子耦合电子转移流形指出，氧化还原非无辜配体作为一种设计元素，可将配位诱导键弱化化学扩展到元素周期表中的更多元素。
