Coordination-induced O-H/N-H Bond Weakening by a Redox Non-innocent, Aluminum-containing Radical

Overview

Journal Nat Commun

Specialty Biology

Date 2024 Feb 13

PMID 38351122

Authors

Soumen Sinhababu

Roushan Prakash Singh

Maxim R Radzhabov

Jugal Kumawat

Daniel H Ess

Neal P Mankad

Affiliations

Soon will be listed here.

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.

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