Dialumene-Mediated Production of Phosphines through P4 Reduction.

The activation and further functionalization of white phosphorus (P4) by main group complexes has become an increasingly studied topic in recent times. Herein, we report the controlled formation of phosphorus-rich alanes featuring butterfly-like geometries from the selective reaction of P4 with dialumenes, ([L(IiPr)Al]2) (1: L = Tripp; 2: L = tBu2MeSi; IiPr = {MeCN(iPr)}2C)). The two-electron-reduction product of P4 features a P42- structure and is shown to be able to act as a source of P3-. Treatments of different electrophiles (e.g., chlorotrimethylsilane (Me3SiCl), iodotrimethylsilane (Me3SiI), HCl, or acetyl chloride (CH3COCl)) with these phosphorus-rich alanes under mild conditions gave the corresponding phosphine (e.g., P(SiMe3)3, PH3, or P(COCH3)).