Dialumene-Mediated Production of Phosphines through P4 Reduction

Huihui Xu; Matthew M D Roy; Arseni Kostenko; John A Kelly; Shiori Fujimori; Shigeyoshi Inoue

doi:10.1002/anie.202404532

Dialumene-Mediated Production of Phosphines through P4 Reduction

Angew Chem Int Ed Engl. 2024 May 19:e202404532. doi: 10.1002/anie.202404532. Online ahead of print.

Authors

Huihui Xu¹, Matthew M D Roy¹, Arseni Kostenko¹, John A Kelly¹, Shiori Fujimori¹, Shigeyoshi Inoue²

Affiliations

¹ Technical University of Munich, Department of Chemistry, GERMANY.
² Technische Universitat Munchen, Department of Chemistry, Lichtenbergstraße 4, 85748 Garching, 85748, Garching bei München, GERMANY.

PMID: 38763910
DOI: 10.1002/anie.202404532

Abstract

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)).

Keywords: Dialumene; P4; aluminum dihalide; phosphines.