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Facile proton-coupled electron transfer enabled by coordination-induced E–H bond weakening to boron


We report the facile activation of aryl E-H (ArEH; E = N, O, S; Ar = Ph or C6F5) or ammonia N-H bonds via coordination-induced bond weakening to a redox-active boron center in the complex, (1-). Substantial decreases in E-H bond dissociation free energies (BDFEs) are observed upon substrate coordination, enabling subsequent facile proton-coupled electron transfer (PCET). A drop of >50 kcal mol-1 in H2N-H BDFE upon coordination was experimentally determined.

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