Synthesis, Structure, and Supramolecular Architecture of Benzonitrile and Pyridine Adducts of Bis(pentafluorophenyl)zinc: Pentafluorophenyl–Aryl Interactions versus Homoaromatic Pairing

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• 作者：Eddy Martin ; Claire Spendley ; Andrew J. Mountford ; Simon J. Coles ; Peter N. Horton ; David L. Hughes ; Michael B. Hursthouse ; Simon J. Lancaster
• 刊名：Organometallics
• 出版年：2008
• 出版时间：April 14, 2008
• 年：2008
• 卷：27
• 期：7
• 页码：1436 - 1446
• 全文大小：1764K
• 年卷期：v.27,no.7(April 14, 2008)
• ISSN：1520-6041

文摘

Treatment of (C₆F₅)₂Zn(toluene) with 2 equiv of a series of benzonitrile or pyridine derivatives yielded the complexes (C₆F₅)₂Zn(L)₂ (where L = benzonitrile, 4-(phenyl)benzonitrile, 4-(N-pyrrolyl)benzonitrile, pyridine, 4-(phenyl)pyridine, and 4-(N-pyrrolyl)pyridine). The four-coordinate solution-phase nature of these complexes was confirmed by a series of variable-temperature ¹⁹F NMR experiments and comparison to (C₆F₅)₂Zn(2,2′-bipy). The solvent-free solid-state structures of each of the four-coordinate adducts and the toluene solvate of (C₆F₅)₂Zn(NCC₆H₄C₆H₅)₂ were determined by single-crystal X-ray diffraction and have distorted tetrahedral geometries. Analysis of the crystal packing revealed a preponderance of offset face-to-face homo−aryl and embrace-like interactions over the hetero−aryl, pentafluorophenyl−phenyl, interaction. These aryl−aryl synthons serve to assemble paired, one- and three-dimensional supramolecular architectures.