Phosphorus(III) cations supported by a PNP pincer ligand and sub-stoichiometric generation of P4 from thermolysis of a nickel insertion product. Academic Article uri icon


  • Neutral, mono-, and dicationic phosphorus(III) compounds are accessible with a supporting PNP pincer ligand (PNP = [4-Me-2-iPr(2)P-C(6)H(3))(2)N]). Reaction of (PNP)H with PCl(3) and nBu(3)N furnished (PNP)PCl(2) (1), which displays a highly temperature-dependent structure in solution. Synthesis and characterization by NMR spectroscopy and X-ray crystallography of Cl/Br-scrambled derivatives, a monocationic derivative [(PNP)PCl][HCB(11)H(11)] (4), and the dicationic derivatives [(PNP)P][OTf](2) (5), [(PNP)P][B(C(6)F(5))(4)](2) (6), [(PNP)P][B(12)Cl(12)] (7) established that 1 not only undergoes several fluxional processes in solution but also possesses a temperature-dependent ground state structure. Reaction of 1 with a Ni(0) source initially leads to a phosphine-phosphinidene complex, followed by thermal generation of P(4).

published proceedings

  • Chemistry

author list (cited authors)

  • Herbert, D. E., Miller, A. D., & Ozerov, O. V.

citation count

  • 16

complete list of authors

  • Herbert, David E||Miller, Adam D||Ozerov, Oleg V

publication date

  • June 2012