European Journal of Inorganic Chemistry
European Journal of Inorganic Chemistry
4 years ago

Halogenated closo-Dodecaborate Anions Stabilize Weakly Bound [(Me3NH)3X]2+ (X = Cl, Br) Dications in the Solid State

Halogenated closo-Dodecaborate Anions Stabilize Weakly Bound [(Me3NH)3X]2+ (X = Cl, Br) Dications in the Solid State
Carsten Jenne, Christoph Bolli, Janis Derendorf, Mathias Keßler
Cocrystallization of [Me3NH]2[B12Y12] (Y = Cl, Br, I) with 1 equiv. of [Me3NH]X (X = Cl, Br) from acetonitrile/diethyl ether solution produced large colorless single crystals of [(Me3NH)3X][B12Y12]. Four different compounds of this type were prepared and structurally characterized. The compounds consist of weakly coordinating perhalogenated closo-dodecaborate [B12Y12]2– dianions and unprecedented weakly bound discrete [(Me3NH)3X]2+ dications. The [(Me3NH)3X]2+ dications are built up from a central halide anion and three [Me3NH]+ cations bound by N–H···X hydrogen bonds. The cations have a pyramidal structure, as determined by X-ray diffraction, which is in contrast to quantum-chemical calculations, which predict a trigonal-planar structure. While the [(Me3NH)3Cl]2+ and [(Me3NH)3Br]2+ cations were easily prepared, attempts to synthesize the corresponding [(Me3NH)3F]2+ and [(Me3NH)3I]2+ cations failed. Three further crystal structures containing the angulated [(Me3NH)2X]+ cation stabilized by [B12Cl12]2–, [B12Br12]2–, or [Me3NB12Cl11]– are reported as well. Unprecedented [(Me3NH)3X]2+ dications are lattice-stabilized in the solid state by perhalogenated closo-dodecaborates. Syntheses of the materials and their crystal structures are discussed and compared with the results of quantum-chemical calculations.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/ejic.201700620

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