Past exam of the chemistry B course of the University of Cambridge 2025 Paper 2 B9 a Solution 2026-10-20
The six P–N bonds are not well described as three permanently localized single bonds alternating with three ordinary double bonds. The strongly polar P–N framework has contributions from ionic bonding and nitrogen lone pair donation into neighboring phosphorus-centered acceptor combinations, including P–Cl orbitals. This negative hyperconjugation supplies additional P–N bonding and equivalent environments around the ring. Approximate planarity is compatible with these interactions, but equal lengths and planarity alone do not establish benzene-like aromaticity. Large phosphorus participation is not required.[ref]
Gallium binds to a ring nitrogen, and the two P–N bonds flanking that nitrogen lengthen. Formation of the NGaCl coordinate covalent bond changes the available nitrogen electron density and local geometry, weakening its contribution to the adjacent P–N interactions. The other four P–N bonds retain greater multiple-bond character and are correspondingly shorter. Loss of the threefold equivalence and altered local geometry permit the ring to pucker. This is a Lewis acid-base adduct, not replacement of a P–Cl bond by GaCl. Single-crystal structures and variable-temperature multinuclear nuclear magnetic resonance establish this class of nitrogen-bound group-13 adducts.[ref]
Group 13 Lewis acid adducts of [PCl2N]3 by Zin-Min Tun and others. 2011, pp. 8937–8945, adduct structures and variable-temperature NMR
Zin-Min Tun Created 2026-10-20 Updated 2026-11-05
Zin-Min Tun investigated Lewis acid adducts of a cyclic phosphazene with group13 compounds. Crystallography and variable-temperature multinuclear NMR spectroscopy characterized the prepared adducts, giving structural evidence about coordination to the ring.[ref]
Group 13 Lewis acid adducts of [PCl2N]3 by Zin-Min Tun and others. 2011, Inorganic Chemistry50,8937–8945: prepared adducts and characterization; no direct high-temperature intermediate claim