A coupled-cluster approach to the relative strains in [1.1.1]propellane, its derivatives and hetero[1.1.1]propellanes
A coupled-cluster approach to the relative strains in [1.1.1]propellane, its derivatives and hetero[1.1.1]propellanes
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[1.1.1]丙烷及其衍生物和杂[1.1.1]丙烷相关菌株的耦合聚类方法
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发表时间：
2012
期刊：
影响因子：
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通讯作者：
C. Pittman
中科院分区：
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作者：
Hanying Xu;S. Saebo;C. Pittman
本文采用增广极化双zeta基组，在耦合团簇单、双水平上对螺桨烷分子[1.1.1]及其中性硼、氮、氧、硫、S-O和SO_2类似物以及甲基、六氟和三羰基取代衍生物进行了理论计算.对每种分子的几何构型进行了优化，并进行了振动分析。本研究的主要目的是确定这些系统中的相对应变，这反过来又是稳定性和反应性的预测因子，提供有关潜在可行合成靶标的有价值信息。具有最小应变的系统是氮、硼和S-O类似物，而SO2取代的分子和六氟和三羰基取代的类似物表现出最大量的应变。几何特征也进行了研究，它表明，非键排斥相互作用的贡献显着的一些系统中的应变，因为笼状结构的力量相对较短的非键距离。
The molecule [1.1.1]propellane and its neutral boron, nitrogen, oxygen, sulphur, S–O, and SO2 analogs as well as the methyl, hexafluoro, and tri-carbonyl substituted derivatives have been investigated by theoretical calculations at the coupled-cluster singles and doubles level with an augmented polarized double zeta basis set. The geometries were optimized and vibrational analysis was carried out for each species. The main objective of this study was to determine the relative strain in these systems, which in turn is a predictor of stability and reactivity providing valuable information about potentially viable synthetic targets. The systems with the least strain are the nitrogen, boron and the S–O analogs, whereas the SO2 substituted molecule and the hexafluoride and tricarbonyl substituted analogs exhibited the largest amount of strain. Geometrical features are also investigated and it is demonstrated that non-bonded repulsive interactions contribute significantly to the strain in some of the systems since cage-like structures force relatively short non-bonded distances.