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首页> 外文期刊>Chemistry: A European journal >Chlorobis(pentafluoroethyl)phosphane: Improved synthesis and molecular structure in the gas phase
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Chlorobis(pentafluoroethyl)phosphane: Improved synthesis and molecular structure in the gas phase

机译：氯双（五氟乙基）膦：改进的气相合成和分子结构

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(C_2F_5)_2PCl is now accessible through a significantly improved synthesis protocol starting from the technical product (C_2F_5)_3PF_2. (C_2F _5)_3PF_2 was reduced in the first step with NaBH_4 in a solvent-free reaction at 120 °C. The product, P(C _2F_5)_3, was treated with an excess of an aqueous sodium hydroxide solution to afford the corresponding phosphinite salt Na ~+(C_2F_5)_2PO~- selectively under liberation of pentafluoroethane. Subsequent chlorination with PhPCl _4 resulted in the selective formation of (C_2F _5)_2PCl, which was isolated by fractional condensation in an overall yield of 66 %. The gas electron diffraction (GED) pattern for (C _2F_5)_2PCl was recorded and found to be described by a two-conformer model. A quantum chemical investigation of the potential-energy surface revealed the possible existence of many low-energy conformers, each with a number of low-frequency vibrational modes and therefore large-amplitude motions. The conformer calculated to be most stable was also found to be most abundant by GED and comprised 61(5) % of the total. The molecular structure parameters determined by GED were in good agreement with those calculated at the MP2/TZVPP level of theory; the only significant difference was a discrepancy of about 3° in the C-P-C angle, which, for the lowest-energy conformer, was refined to 98.2(4)° and was calculated to be 94.9°.
机译：（C_2F_5）_2PC1现在可以通过从技术产品（C_2F_5）_3PF_2开始的显着改进的合成协议访问。在第一步中，在无溶剂的情况下，用NaBH_4还原（C_2F _5）_3PF_2。将产物P（C _2F_5）_3用过量的氢氧化钠水溶液处理，以在五氟乙烷释放下选择性地提供相应的次膦酸盐Na〜+（C_2F_5）_2PO_-。随后用PhPC1-4氯化导致选择性形成（C_2F _5）_2PC1，通过分步冷凝将其分离，总产率为66％。记录了用于（C _2F_5）_2PC1的气体电子衍射（GED）模式，并发现该模式由二聚体模型描述。对势能表面进行的量子化学研究表明，可能存在许多低能构象体，每个构象体都有许多低频振动模式，因此具有大振幅运动。通过GED还发现计算出最稳定的构象异构体最丰富，占总数的61（5）％。通过GED测定的分子结构参数与理论上在MP2 / TZVPP水平上计算的参数相吻合;唯一的显着差异是C-P-C角大约有3°的差异，对于最低能量的构象异构体，该角度已精炼为98.2（4）°，计算得出为94.9°。

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