Direct electrochemical P(V) to P(III) reduction of phosphine oxide facilitated by triaryl borates,Journal of the American Chemical Society

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Direct electrochemical P(V) to P(III) reduction of phosphine oxide facilitated by triaryl borates
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-10-02 , DOI: 10.1021/jacs.8b07149
Joseph S. Elias ₁ , Cyrille Costentin _{1,

2} , Daniel G. Nocera ₁

Affiliation

Triaryl borate Lewis acids facilitate the direct two-electron reduction of the P(V) center of triphenylphosphine oxide (TPPO) to the P(III) center of triphenylphosphine at faradaic efficiencies of 37%. Insight from direct P(V) to P(III) reduction is provided from cyclic voltammetry. The electrochemical reduction of TPPO proceeds through 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, with tris(4-methoxyphenyl) borate demonstrating the highest for both. These results suggest that an attractive route toward 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.

中文翻译：

三芳基硼酸盐促进氧化膦的直接电化学 P(V) 到 P(III) 还原

三芳基硼酸盐路易斯酸以 37% 的法拉第效率促进三苯基氧化膦 (TPPO) 的 P(V) 中心直接双电子还原到三苯基膦的 P(III) 中心。循环伏安法提供了从 P(V) 到 P(III) 直接还原的洞察力。TPPO 的电化学还原通过一种不寻常的 ECrECi 机制进行，在该机制中，与硼酸三芳基酯的双电子还原缔合复合物中的磷酰基键断裂是速率决定性的。TPPO 还原的速率和法拉第效率通过明智选择硼酸三芳基酯上的取代基来调节，其中三（4-甲氧基苯基）硼酸酯表现出两者最高。

更新日期：2018-10-02

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