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Updated: May 10, 2026

A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes
Published on: February 27, 2017
Crystal structure determination of the nonclassical 2-norbornyl cation
F Scholz1, D Himmel, F W Heinemann
1Institut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität Freiburg, Freiburg, Germany.
Abstract:
After decades of vituperative debate over the classical or nonclassical structure of the 2-norbornyl cation, the long-sought x-ray crystallographic proof of the bridged, nonclassical geometry of this prototype carbonium ion in the solvated [C7H11](+)[Al2Br7](-) • CH2Br2 salt has finally been realized. This achievement required exceptional treatment. Crystals obtained by reacting norbornyl bromide with aluminum tribromide in CH2Br2 undergo a reversible order-disorder phase transition at 86 kelvin due to internal 6,1,2-hydride shifts of the 2-norbornyl cation moiety. Cooling with careful annealing gave a suitably ordered phase. Data collection at 40 kelvin and refinement revealed similar molecular structures of three independent 2-norbornyl cations in the unit cell. All three structures agree very well with quantum chemical calculations at the MP2(FC)/def2-QZVPP level of theory.
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