Selective Functionalization of P4 by Metal-Mediated CP Bond Formation

A new and selective one‐step synthesis was developed for the first activation stage of white phosphorus by organic radicals. The reactions of NaCpR with P4 in the presence of CuX or FeBr3 leads to the clean formation of organic substituted P4 butterfly compounds CpR2P4 (CpR: CpBIG=C5(4‐nBuC6H4)5 (1 a), Cp′′′=C5H2tBu3 (1 b), Cp*=C5Me5 (1 c) und Cp4iPr=C5HiPr4 (1 d)). The reaction proceeds via the activation of P4 by CpR radicals mediated by transition metals. The newly formed organic derivatives of P4 have been comprehensively characterized by NMR spectroscopy and X‐ray crystallography. New wings for the P4 butterfly: Using two methods starting from white phosphorus, the carbon‐substituted bicyclic P4 butterfly compounds CpR2P4 (CpR=C5(4‐nBuC6H4)5, C5H2tBu3, C5Me5, C5HiPr4) were generated. The methods involve the intermediary formation of {CpR} radicals that selectively open one PP bond of the P4 tetrahedron. The simple procedures and the broad variety of suitable CpR substituents open new ways in the carbon‐based P4 activation.