Li Wei-Qi, Tian Wei-Quan, Feng Ji-Kang, Liu Zi-Zhong, Ren Ai-Min, Sun Chia-Chung, Aoki Yuriko
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China.
Department of Material Sciences, Faculty of Engineering Sciences, Kyushu University, 6-1 Kasugakoen, Kasuga, Fukuoka 816-8580, Japan.
J Comput Chem. 2007 Jul 15;28(9):1467-1475. doi: 10.1002/jcc.20650.
Calculations with B3LYP within quantum chemical density functional theory have been carried out for 1-H-phosphininium cation and a series of 1-R-phosphininium molecules (R=cyclopentadiene, alpha and beta pyrroles, alpha and beta phosphole, C5BH5-- and CH2--). The negative nuclear-independent chemical shift values and the positive aromatic stabilization energies confirm that they are aromatic compounds. In particular, the 1-H-phosphininium cation even exhibits stronger aromatic character than the well-known aromatic phosphinine. The aromatic substituents have strong capability to attract electrons. It is the conjugation and aromaticity that keeps the stability and conformations of the molecules investigated. Owing to the perturbation of the aromatic substituted groups, the predicted large T values and the enlarged HOMO-LUMO gap of the phosphininium cation indicate that these compounds are expected in experiment.
采用量子化学密度泛函理论中的B3LYP方法，对1 - H - 磷鎓阳离子以及一系列1 - R - 磷鎓分子（R = 环戊二烯、α和β吡咯、α和β磷杂环戊二烯、C5BH5 - 和CH2 - ）进行了计算。负的核独立化学位移值和正的芳香稳定能证实它们是芳香化合物。特别地，1 - H - 磷鎓阳离子甚至表现出比著名的芳香磷杂苯更强的芳香性。芳香取代基具有很强的吸电子能力。正是共轭和芳香性保持了所研究分子的稳定性和构象。由于芳香取代基的扰动，预测的磷鎓阳离子的大T值和扩大的HOMO - LUMO能隙表明这些化合物有望在实验中得到。
