Optimized Synthesis of Tetrafluoroterephthalic Acid: A Versatile Linking Ligand for the Construction of New Coordination Polymers and Metal-Organic Frameworks

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• 作者：Andreas Orthaber ; Christiane Seidel ; Ferdinand Belaj ; Jrg H. Albering ; Rudolf Pietschnig ; Uwe Ruschewitz
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：October 18, 2010
• 年：2010
• 卷：49
• 期：20
• 页码：9350-9357
• 全文大小：912K
• 年卷期：v.49,no.20(October 18, 2010)
• ISSN：1520-510X

文摘

Pure 2,3,5,6-tetrafluoroterephthalic acid (H₂tfBDC) is obtained in high yields (95%) by reacting 1,2,4,5-tetrafluorobenzene with a surplus (>2 equiv) of n-butyllithium in tetrahydrofuran (THF) and subsequent carbonation with CO₂ without any extensive purification procedure. A single crystal X-ray structure analysis of H₂tfBDC (1) confirms former data obtained for a deuterated sample (P, Z = 1). Recrystallization from water/acetone leads to single crystals of H₂tfBDC·2H₂O (2, P2₁/c, Z = 2), where an extensive hydrogen bonding network is found. By reacting H₂tfBDC with an aqueous ammonia solution, single crystals of (NH₄)₂tfBDC (3, C2/m, Z = 2) are obtained. 3 is thermally stable up to 250 °C and shows an enhanced solubility in water compared to H₂tfBDC. Monosubstituted 2,3,5,6-tetrafluorobenzoic acid (H₂tfBC, 4) is obtained by reacting 1,2,4,5-tetrafluorobenzene with stoichiometric amounts (1 equiv) of n-butyllithium in THF. Its crystal structure (Fdd2, Z = 16) shows dimeric units as characteristic structural feature.