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DOI: 10.1055/s-0030-1259529
TMSCl-Promoted Electroreduction of Triphenylphosphine Oxide to Triphenylphosphine
Publication History
Publication Date:
08 February 2011 (online)

Abstract
Direct reductive transformation of triphenylphosphine oxide to triphenylphosphine was performed successfully by electrolysis with TMSCl in an acetonitrile/Bu4NBr/(Zn anode)-(Pt cathode)/undivided cell/constant current electrolysis system. A plausible ECEC mechanism involving the formation of silylated phosphorus radical is proposed.
Key words
reduction - electron transfer - phosphorus - silicon
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References and Notes
No appreciable difference in chemical shifts between ³¹P NMR spectra of triphenylphosphine oxide 2 (d = 26.2 ppm in MeCN) and that of a mixture of 2 and TMSCl (1:1) was observed, suggesting that any reactions of 2 with TMSCl would not occur before electrochemical reduction of 2.
17Though the reaction conditions were not optimized yet, other triarylphosphines such as tris(o-toryl)phosphine, tris(m-toryl)phosphine, and tris(p-toryl)phosphine were obtained from the corresponding phosphine oxides in 58%, 74%, and 78% yield, respectively.