Novel tetraaminophosphonium salts by anion exchange in liquid ammonia

[P(NH2)(4)]Br and [P(NH2)(4)][NO3] have been prepared by anion exchange in liquid ammonia. Single crystals of [P(NH2)(4)]Br were obtained from an acet onitrile solution in a temperature gradient between 60 degrees C and room t emperature while attempts to grow single crystals of [P(NH2)(4)][NO3] yield ed [P(NH2)(4)][NO3](OP(NH2)(3)). Both crystal structures were determined by single crystal X-ray methods at room temperature ([P(NH2)(4)]Br: P4/nbm, a = 809.2(1), c = 468.1(1) pm, Z = 2, R1 = 0.042, wR2 = 0.077; [P(NH2)(4)][N O3](OP(NH2)(3)): Pna2(1), Z = 4, a = 1023.4(1), b = 1704.7(1), c = 618.0(1) pm, R1 = 0.025, wR2 = 0.067. In the solid [P(NH2)(4)]Br forms a tetragonal ly distorted variant of the CsCl type of structure. [P(NH2)(4)][NO3](OP(NH2 )(3)) consists of [P(NH2)(4)](+) cations, [NO3](-) anions, and OP(NH2)(3) m olecules which are interconnected by a complex system of hydrogen bonds.