Preparation and Properties of Dimethyltetrafluorophosphate

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• 作者：Christian Hohenstein ; Andreas Kornath ; Frank Neumann ; Ralf Ludwig
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：July 19, 2010
• 年：2010
• 卷：49
• 期：14
• 页码：6421-6427
• 全文大小：742K
• 年卷期：v.49,no.14(July 19, 2010)
• ISSN：1520-510X

文摘

Dimethyltrifluorophosphorane reacts with strong fluoride donors, such as CsF, Me₄NF, and Me₄PF, under formation of dimethyltetrafluorophosphates. The salts were characterized by infrared and Raman spectroscopy and in acetonitrile solutions by NMR spectroscopy. The experimental results show that only the trans isomer is formed. Theoretical calculations (B3LYP/6-31+G* and RHF/6-31+G*) of the trans and cis isomer yielded a difference of the Gibbs free energy of 29.4 kJ/mol (B3LPY/6-31+G*). The Me₄N⁺[Me₂PF₄]⁻ crystallizes in the orthorhombic space group Pnma with four formula units per unit cell and dimensions of a = 1303.5(3), b = 799.8(2), and c = 1023.8(4) pm. The phosphorus atom has an octahedral environment with P−C distances of 183.4(3) pm and P−F bond lengths in the range between 166.1(1) and 168.2(1) pm. In the crystal packing, anions and cations are linked via weak fluorine hydrogen contacts forming a three-dimensional network.