[(HBNPEt_3)]_4NPEt_3]Br_3 (1) has been prepared by the reaction of Me_3SiNPEt_3 with [HBBr_2(SMe_2)] in dichloromethane solution at 20 deg C. According to ~(11)B-NMR and ~(31)PNMR spectroscopy and to a crystal structure determination the cation of 1 has the structure of a bicyclic penta(phosphorano)borazinium-trication. 1 centre dot 3 CH_2Cl_2: Space group P2_12_12_1, Z = 8, lattice dimensions at -83 deg C: a = 2124.8(1), b = 2307.6(1), c = 2323.1(1) pm, R_1 = 0.0733.
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