title: Phosphorus(III) cations supported by a PNP pincer ligand and sub-stoichiometric generation of P4 from thermolysis of a nickel insertion product.
abstract: 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).
authors.affiliation: Department of Chemistry, Texas A&M University, College Station, TX 77842, USA.
authors.forename: David E
authors.initials: DE
authors.lastname: Herbert
authors.forename: Adam D
authors.initials: AD
authors.lastname: Miller
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Ozerov