Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer† †Electronic supplementary information (ESI) available. CCDC 1882890–1882892. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc05657a

Acyl(chloro)phosphines RC(O)P(Cl)( t -Bu) have been prepared by formal insertion of tert -butyl phosphinidene ( t -Bu–P) from t -BuP A ( A = C 14 H 10 or anthracene) into the C–Cl bond of acyl chlorides. Acyl(chloro)phosphines RC(O)P(Cl)( t -Bu) have been prepared by formal insertion of tert -butyl phosphinidene ( t -Bu–P) from t -BuP A ( A = C 14 H 10 or anthracene) into the C–Cl bond of acyl chlorides. We show that the under-explored acyl(chloro)phosphine functional group provides an efficient method to prepare bis(acyl)phosphines, which are important precursors to compounds used industrially as radical polymerization initiators. Experimental and computational investigations into the mechanism of formation of acyl(chloro)phosphines by our synthetic method reveal a pathway in which chloride attacks a phosphonium intermediate and leads to the reductive loss of anthracene from the phosphorus center in a P( v ) to P( iii ) process. The synthetic applicability of the acyl(chloro)phosphine functional group has been demonstrated by reduction to an acylphosphide anion, which can in turn be treated with an acyl chloride to furnish dissymmetric bis(acyl)phosphines.