Bicapped square antiprism 2026-10-20
For E, each BH supplies two skeletal electrons and each phosphorus vertex supplies three after retaining a lone pair. Hence electrons, or thirteen pairs, matching a twelve-vertex closo cluster. Place the two adjacent P vertices on a regular icosahedron. The remaining ten boron vertices fall into four symmetry classes: two sites adjacent to both P vertices, four adjacent to exactly one, two adjacent to neither but opposite the common-neighbour pair, and two opposite the P pair. The populations are , so four boron resonances are expected. Interchanging the identical phosphorus vertices is allowed when determining chemical equivalence.
For F, a ten-vertex bicapped square antiprism offers a consistent closo model. There are eight BH vertices, one B vertex bearing the donor instead of H, and one P vertex. Their skeletal contributions are respectively , and , giving 22 electrons, eleven pairs. The donor-bearing B contribution follows from B plus the donated lone pair minus the exoskeletal B–N bond, .
One explicit arrangement consistent with six boron signals puts P at one axial cap and the substituent on one B vertex of the nearer square. The remaining mirror plane through that B, the opposite vertex of its square, and the cap axis leaves three B sites individually fixed: the donor-bearing B, its opposite square vertex and the other axial cap. The other six B sites form three exchanged pairs. Thus the nine borons give three singleton environments and three two-site environments, six signals in all. The original compound has a crystallographically characterized positional assignment; the spectrum alone asks for a compatible structure and does not establish a unique positional isomer. A single-crystal X-ray diffraction determination or assigned heteronuclear correlations would distinguish alternatives.[ref]
Synthesis of polyhedral phosphaboranes: crystal structure of 6-(C2H5)3N·2-PB9H8 by John L. Little and others. 1989, pp.1087–1091, synthesis of diphosphaborane and crystallographic characterization of the amine-containing side product
