P4 functionalization by hydrides: direct synthesis of P-H bondsElectronic supplementary information (ESI) available: Experimental procedures and characterizations of compounds. CCDC 1423489. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6cc01683a

A direct method for white phosphorus functionalization by hydride sources is presented. Excess BH 4 − in n -butylamine produces HP 4 − as the major P-containing species. Reaction with LiBEt 3 H forms the borane-stabilized phosphanide Li(PH 2 )(BEt 3 ) 2 , which may be used to synthesize various phosphines. Triethylborane may be replaced by BH 3 , resulting in the formation of LiPH 2 (BH 3 ) 2 . Functionalization of white phosphorus (P 4 ) by hydride sources MBH 4 and LiBEt 3 H leads to the formation of HP 4 M and LiPH 2 (BEt 3 ) 2 respectively.