Faculty of Chemistry, University of the Basque Country UPV/EHU, and Donostia International Physics Center (DIPC), P.K. 1072, 20080, Donostia, Spain.
J Phys Chem A. 2013 Apr 18;117(15):3243-51. doi: 10.1021/jp4016933. Epub 2013 Apr 8.
A theoretical study of the complexes between dihydrogen, H2, and a series of amine, phosphine, and arsine derivatives (ZH3 and ZH2X, with Z = N, P, or As and X = F, Cl, CN, or CH3) has been carried out using ab initio methods (MP2/aug-cc-pVTZ). Three energetic minima configurations have been characterized for each case with the H2 molecule in the proximity of the pnictogen atom (Z). In configuration A, the σ-electrons of H2 interact with σ-hole region of the pnictogen atom generated by the of X-Z bond. These complexes can be ascribed as pnictogen bonded. In configuration C, the lone electron pair of Z acts as the Lewis base, and H2 plays the role of the Lewis acid. Finally, configuration B presents a variety of noncovalent interactions depending on the binary complex considered. The atoms-in-molecules theory (AIM), natural bond orbitals (NBO) method as well as the density functional theory-symmetry adapted perturbation theory (DFT-SAPT) approach were used in this study to deepen the nature of the interactions considered.
采用从头算方法（MP2/aug-cc-pVTZ）对一系列胺、膦和胂衍生物（ZH3 和 ZH2X，其中 Z = N、P 或 As，X = F、Cl、CN 或 CH3）与氢气（H2）形成的配合物进行了理论研究。对于每种情况，H2 分子都靠近磷属元素原子（Z），都有三种能量最低的稳定构型。在构型 A 中，H2 的σ 电子与由 X-Z 键生成的磷属元素原子的σ 空穴区域相互作用。这些配合物可以被归为磷属元素键合。在构型 C 中，Z 的孤对电子充当路易斯碱，而 H2 则充当路易斯酸。最后，构型 B 则根据所考虑的二元配合物呈现出各种非共价相互作用。本研究中使用了原子在分子中的理论（AIM）、自然键轨道（NBO）方法以及密度泛函理论-对称适应微扰理论（DFT-SAPT）方法，以深入研究所考虑的相互作用的本质。
