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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Synthesis, Microwave Spectrum, Quantum Chemical Calculations, and Conformational Composition of a Novel Primary Phosphine, Cyclopropylethynylphosphine, (C_3H_5C≡CPH_2)
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Synthesis, Microwave Spectrum, Quantum Chemical Calculations, and Conformational Composition of a Novel Primary Phosphine, Cyclopropylethynylphosphine, (C_3H_5C≡CPH_2)

机译：新型伯膦环丙基乙炔基膦（C_3H_5C≡CPH_2）的合成，微波光谱，量子化学计算和构象组成

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The microwave spectrum of cyclopropylethynylphosphine, C_3H_5C≡CPH_2, has been investigated in the 26-120 GHz spectral region. The spectrum is dominated by very rich and complex a-type R-branch pile-ups. There must be insignificant steric interaction between the phosphino group and the cyclopropyl ring due to the long distance between these two groups. However, the phosphino group does not undergo free or nearly free internal rotation. Instead, the spectra of two distinct conformers were assigned. Both these two forms have C_S symmetry. The symmetry plane bisects the cyclopropyl ring and the phosphino group in both conformers, and the lone electron pair of the phosphino group points in opposite directions in the two rotamers. The energy difference between the two forms was determined to be 1.9(6) kJ/mol. A simple model that takes into consideration the interaction of the lone electron pair of the phosphino group with the π-electrons of the ethynyl group and the Walsh electrons of the cyclopropyl ring is able to give a qualitative explanation of the observation of two conformers and the nonexistence of free rotation of the phosphino group. The MW work was augmented by quantum chemical calculations using second-order M?ller-Plesset perturbation and coupled cluster theory with results that are in good agreement with the experiments.
机译：在26-120 GHz光谱范围内研究了环丙基乙炔基膦C_3H_5C 26CPH_2的微波光谱。频谱以非常丰富和复杂的a型R分支堆积为主导。由于这两个基团之间的距离很长，膦基与环丙基之间必须没有明显的空间相互作用。然而，膦基基团不经历自由或几乎自由的内部旋转。而是分配了两个不同构象体的光谱。这两种形式都具有C_S对称性。对称平面将两个构象中的环丙基环和膦基二等分，并且膦基的孤电子对在两个旋转异构体中指向相反的方向。两种形式之间的能量差确定为1.9（6）kJ / mol。一个简单的模型考虑了膦基的孤电子对与乙炔基的π电子和环丙基环的沃尔什电子的相互作用，可以定性解释观察到的两个构象异构体。不存在膦基的自由旋转。通过使用二阶M？ller-Plesset摄动和耦合簇理论的量子化学计算，增加了MW的工作，其结果与实验非常吻合。

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