Phosphorus Heterocycles from Sodium Dihydrogen Phosphide: Simple Synthesis and Structure of 3,5‐Diphenyl‐2,4‐diazaphospholide

The mixed phosphide‐alkoxide aggregate [Na 5 (O t Bu) 4 PH 2 ] · dme is readily available by reacting first red phosphorus with sodium metal in dimethoxyethane (dme) in presence of 5 mol‐% naphthalene and then adding tert ‐butanol. [Na 5 (O t Bu) 4 PH 2 ] · dme is a suitable reagent for the direct synthesis of heterocyclic phosphorus compounds like sodium isophosphindolin‐1,3‐dionide, [Na{P(CO) 2 C 6 H 4 }] and sodium 3,5‐diphenyl‐1,2,4‐diazaphospholide, [Na{P(CPh) 2 N 2 }]. The latter was characterized by a X‐ray diffraction study as a one dimensional coordination polymer [Na(dme){P(CPh) 2 N 2 }] ∞ .