The bis(Biphenyl)phosphorus Fragment in Trivalent and Tetravalent P-Environments

Diaryl substituted phosphorus (III) compounds are commonly used motifs in synthesis. Although the basic synthetic routes to these molecules starting from PCl3 well reported, sterically hindered aryl substituents can be difficult introduce, especially if P atom is ortho position another group. This work explores chemistry of bis(biphenyl)phosphorus(III) fragment. As third substituents, H, M, Cl, NR2, two group 14 element and also Li were introduced high-yielding processes offering a wide chemical variety bis(biphenyl) phosphine motif. In addition, tetravalent borane adduct was isolated. All structures thoroughly investigated by heteronuclear NMR spectroscopic analysis. Furthermore, reaction conditions discussed connection with four crystal aminophosphine, phosphine, phosphide provided. The latter crystallized as dimer unique planar P2Li2 ring, which stabilized non-covalent C⋯Li interaction arising biphenyl motif represents rare example donor-free ring.