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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >The molecular structure of tetra-tert-butyldiphosphine: an extremely distorted, sterically crowded molecule
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The molecular structure of tetra-tert-butyldiphosphine: an extremely distorted, sterically crowded molecule

机译：四叔丁基二膦的分子结构：高度扭曲，空间拥挤的分子

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The molecular structure of tetra-tert-butyldiphosphine has been determined in the gas phase by electron diffraction using the new DYNAMITE method and in the crystalline phase by X-ray diffraction. Ab initio methods were employed to gain a greater understanding of the structural preferences of this molecule in the gas phase, and to determine the intrinsic P-P bond energy, using recently described methods. Although the P-P bond is relatively long [GED 226.4(8) pm; X-ray 223.4(1) pm] and the dissociation energy is computed to be correspondingly small (150.6 kJ mol(-1)), the intrinsic energy of this bond (258.2 kJ mol(-1)) is normal for a diphosphine. The gaseous data were refined using the new Edinburgh structure refinement program ed@ed, which is described in detail. The molecular structure of gaseous P2Bu4t is compared to that of the isoelectronic 1,1,2,2-tetra-tert-butyldisilane. The molecules adopt a conformation with C-2 symmetry. The P-P-C angles returned from the gas electron diffraction refinement are 118.8(6) and 98.9(6)degrees, a difference of 20degrees, whilst the C-P-C angle is 110.3(8)degrees. The corresponding parameters in the crystal are 120.9(1), 99.5(1) and 109.5(1)degrees. There are also large deformations within the tert-butyl groups, making the DYNAMITE analysis for this molecule extremely important.
机译：四叔丁基二膦的分子结构已在气相中使用新的DYNAMITE方法通过电子衍射测定，在结晶相中通过X射线衍射测定。使用了从头算的方法，可以使用最近描述的方法来更好地理解该分子在气相中的结构偏好，并确定其固有的P-P键能。尽管P-P键相对较长[GED 226.4（8）pm; X射线223.4（1）pm]，并且计算出离解能相应较小（150.6 kJ mol（-1）），该键的本征能（258.2 kJ mol（-1））对于二膦是正常的。使用新的爱丁堡结构改进程序ed @ ed对气态数据进行了详细描述。将气态P2Bu4t的分子结构与等电子1,1,2,2-四叔丁基乙硅烷的分子结构进行了比较。分子采用具有C-2对称性的构象。从气相电子衍射细化返回的P-P-C角分别为118.8（6）和98.9（6）度，相差20度，而C-P-C角为110.3（8）度。晶体中的相应参数为120.9（1），99.5（1）和109.5（1）度。叔丁基内还存在较大的形变，因此对该分子的DYNAMITE分析极为重要。

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