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

Polyborate Anions Partnered with Large Nonmetal Cations: Triborate(1–), Pentaborate(1–) and Heptaborate(2–) Salts

Polyborate Anions Partnered with Large Nonmetal Cations: Triborate(1–), Pentaborate(1–) and Heptaborate(2–) Salts
Peter N. Horton, Michael A. Beckett, Charlotte L. Jones, Simon J. Coles
New polyborate salts containing bulky nonmetal cations have been prepared from either the free organic base or the [nonmetal cation][OH] in an aqueous solution with methanol: 1-adamantylammonium pentaborate [C10H18N][B5O6(OH)4] (1), 2-adamantylammonium pentaborate dihydrate [C10H18N][B5O6(OH)4]·2H2O (2), N,N-dimethyl-1-adamantylammonium pentaborate boric acid monohydrate [C12H22N][B5O6(OH)4]·B(OH)3·H2O (3), N,N,N-trimethyl-1-adamantylammonium pentaborate trihydrate [C13H24N][B5O6(OH)4]·3H2O (4), N,N,N-trimethyl-2-adamantylammonium pentaborate trihydrate [C13H24N][B5O6(OH)4]·3H2O (5), dibenzylammonium pentaborate sesquihydrate [C14H16N][B5O6(OH)4]·1.5H2O (6), bis(triphenylphosphine)iminium pentaborate sesquihydrate [C36H30NP2][B5O6(OH)4]·1.5H2O (7), bis(triphenylphosphine)iminium triborate·2.5hydrate [C36H30NP2][B3O3(OH)4]·2.5H2O (8), 4,4′-bipiperidinium heptaborate dihydrate [C10H22N2][B7O9(OH)5]·2H2O (9). All compounds were characterized by thermal (TGA/DSC) and spectroscopic (NMR, IR) analysis. Compounds 3–5 and 9 were characterized by single-crystal XRD studies. The waters of crystallization in 3–6 and the boric acid of crystallization in 3 play important structural roles in expanding the supramolecular pentaborate(1–) lattices to accommodate the bulkier cations. Triborate(1–) and heptaborate(2–) anions have been templated by the PPN(1+) and bipiperidinium(2+) cations, respectively, and pentaborate(1–) salts co-crystalized with additional molecules of [H2O/B(OH)3]. The co-crystallized molecules function as “spacer” entities enabling the supramolecular H-bonded anionic lattice to expand in order to accommodate the large cations.

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

DOI: 10.1002/ejic.201700551

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