Synthesis of Stable Potassium Phosphinophosphides and Reaction with Organosilyl Halides and Chlorophosphanes

Szych Lilian Sophie , Lüdtke Karsten Paul, Villinger Alexander, Bockfeld Dird, Tamm Matthias, Schulz Axel

Abstract

The synthesis of sterically demanding 2,6-bis(2,4,6-trimethylphenyl)phenyl (Ter)-stabilized and H-substituted diphosphanes TerHP–PR2 (4a–4c) via conversion of the phosphide TerPHK (2) with secondary chlorophosphanes ClPR2 (3a–3c, where R = iPr, Ph, and tBu, respectively) is described. The diphosphanes 4a–4c were deprotonated using KH in tetrahydrofuran, selectively yielding the potassium phosphinophosphides K[TerP–PR2] (5a–5c). These phosphinophosphides are stable in solution as well as in the solid state and can be further functionalized via salt-metathesis reactions. Reaction with organosilyl halides selectively yields the silylated diphosphanes Ter(SiR12R2)P–P(iPr)2 (6a and 6b, where R1 = R2 = CH3 and R1 = CH3, R2 = Ph, respectively), whereas conversion with chlorophosphanes selectively yields the triphosphanes R12P–P(Ter)–P(iPr)2 (7a and 7b, where R = iPr and Ph, respectively).