From both energy and environmental standpoints of sustainability, it is critical to develop direct methods that can reclaim, recycle, and repurpose P(III) compounds from P(V)-ates. Such a conversion avoids the energy intensive and energy wasting P(V)-ate to P(0) to P(III) conversion of legacy methods. We describe the use of triaryl borate Lewis acids to assist in the direct two-electron reduction of the P(V) oxides to P(III) phosphines via an unusual ECrECi mechanism in which the breaking of the phosphoryl bond in a two-electron-reduced association complex with the triaryl borate is rate-determining. The rate and faradaic efficiency for TPPO reduction are tuned by judicious choice of substituents on triaryl borate. These results suggest that an attractive route towards the room-temperature reduction of phosphate for phosphorus reclamation is greatly facilitated by the stabilization of reduced phosphate intermediates through their association with Lewis acids.

Direct P(V)-ate to P(III) electrocatalytic conversions

2019 Spring National Meeting

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