Solid-state solvation and anion packing patterns in X-ray structures of crystalline K₂(solv)_nB₁₂F₁₂ (solv = H₂O₂(aq), CH₃OH, CH₃NO₂, and CH_3<

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• 作者：Dmitry V. Peryshkov ; Eric V. Bukovsky ; Travis C. Folsom ; Steven H. Strauss ; ^{steven.strauss@colostate.edu}
• 关键词：Fluoroanion ; Superweak anion ; Solid-state solvation ; X-ray structure ; Hydrogen peroxide solvate
• 刊名：Polyhedron
• 出版年：2013
• 出版时间：13 July, 2013
• 年：2013
• 卷：58
• 期：Complete
• 页码：197-205
• 全文大小：1797 K

文摘

Four new solvates of K₂B₁₂F₁₂ have been isolated and structurally characterized, K₂(H₂O₂)₂B₁₂F₁₂, K₂(CH₃OH)₂B₁₂F₁₂, K₂(CH₃NO₂)₂B₁₂F₁₂, and K₂(CH₃CN)₂B₁₂F₁₂. The packing of [K₂(solv)₂]²⁺ cations and B₁₂F₁₂^2? anions are compared with each other, with the previously published solvates K₂(H₂O)₂B₁₂F₁₂, K₂(H₂O)₄B₁₂F₁₂, and K₂(HF)₃B₁₂F₁₂, and with the solvent-free salt K₂B₁₂F₁₂ to explain why the solid-state solvation of K₂B₁₂F₁₂ by some gaseous solvent molecules, including H₂O and CH₃CN, is both thermodynamically favorable and kinetically facile. The compound K₂(H₂O₂)₂B₁₂F₁₂ was found to be energetic and underwent rapid deflagration when scraped with a metal spatula and therefore should only be prepared in small quantities. An alternative procedure for the purification of crude K₂B₁₂F₁₂ that does not involve treatment with aqueous H₂O₂ is described.