Nature Communications (Feb 2024)

Coordination-induced O-H/N-H bond weakening by a redox non-innocent, aluminum-containing radical

  • Soumen Sinhababu,
  • Roushan Prakash Singh,
  • Maxim R. Radzhabov,
  • Jugal Kumawat,
  • Daniel H. Ess,
  • Neal P. Mankad

DOI
https://doi.org/10.1038/s41467-024-45721-1
Journal volume & issue
Vol. 15, no. 1
pp. 1 – 7

Abstract

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Abstract 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.