Intra- and Intermolecular N-H···F-C Hydrogen-Bonding Interactions in Amine Adducts of Tris(pentafluorophenyl)borane and -alane

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• 作者：Andrew J. Mountford ; Simon J. Lancaster ; Simon J. Coles ; Peter N. Horton ; David L. Hughes ; Michael B. Hursthouse ; and Mark E. Light
• 刊名：Inorganic Chemistry
• 出版年：2005
• 出版时间：August 8, 2005
• 年：2005
• 卷：44
• 期：16
• 页码：5921 - 5933
• 全文大小：322K
• 年卷期：v.44,no.16(August 8, 2005)
• ISSN：1520-510X

文摘

The reaction between B(C₆F₅)₃ and NH₃(g) in light petroleum yielded the solvated adduct H₃N·B(C₆F₅)₃·NH₃. Treatmentwith a second equivalent of B(C₆F₅)₃ afforded H₃N·B(C₆F₅)₃. Attempts to prepare the analogous alane adduct wereunsuccessful and resulted in protolysis. Related compounds of the form R'R' 'N(H)·M(C₆F₅)₃ were synthesizedfrom M(C₆F₅)₃ and the corresponding primary and secondary amines (M = B, Al; R' = H, Me, CH₂Ph; R' ' = Me,CH₂Ph, CH(Me)(Ph); R'R' ' = cyclo-C₅H₁₀). The solid-state structures of 13 new compounds have been elucidatedby single-crystal X-ray diffraction and are discussed. Each of the borane adducts has a significant bifurcatedintramolecular hydrogen bond between an amino hydrogen and two o-fluorines, while N-H···F-C interactions inthe alane adducts are weaker and more variable. ¹⁹F NMR studies demonstrate that the borane adducts retain thebifurcated C-F···H···F-C hydrogen bond in solution. Compounds of the type R'R' 'N(H)·M(C₆F₅)₃ conform toEtter's rules for the prediction of hydrogen-bonding interactions.