Wang Haiyan, Liu Feng-Ling
College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Provincial Key Laboratory of Clean Production of Fine Chemicals, Shandong Normal University, Jinan 250014, P. R. China.
ACS Omega. 2020 Sep 18;5(38):24513-24519. doi: 10.1021/acsomega.0c02969. eCollection 2020 Sep 29.
As we know, oxygen usually forms two single bonds with other atoms, whereas in this work, we reported the neutral molecules with square planar O(B)4-type tetracoordinate oxygen substructures. The difficulty to achieve a square planar O(B)4-type arrangement is not only to overcome the strain from the planar to tetrahedral configuration but also to constrain it in a right system with the proper symmetry. Several neutral molecules with square planar O(B)4-type arrangements have been studied using the DFT method at the B3LYP/6-311++G(3df,3pd) level of theory. The computational results show that they are all real minima on potential energy hypersurfaces. Thus, it has been shown theoretically that the square planar O(B)4-type arrangement is achieved. The molecular orbitals among the square planar O(B)4-type substructure at symmetry have been suggested. Using the molecular orbitals, it has been explained that the oxygen 2p -π electrons in the square planar O(B)4-type arrangement are no longer the lone-pair electrons.
如我们所知，氧通常与其他原子形成两个单键，而在本工作中，我们报道了具有平面正方形O(B)4型四配位氧亚结构的中性分子。实现平面正方形O(B)4型排列的困难不仅在于克服从平面构型到四面体构型的应变，还在于将其限制在具有适当对称性的正确体系中。已使用密度泛函理论（DFT）方法在B3LYP/6-311++G(3df,3pd)理论水平上研究了几种具有平面正方形O(B)4型排列的中性分子。计算结果表明，它们都是势能超曲面上的真正极小值。因此，从理论上证明了平面正方形O(B)4型排列是可以实现的。已提出了平面正方形O(B)4型亚结构在特定对称性下的分子轨道。利用这些分子轨道，已解释了平面正方形O(B)4型排列中的氧2p -π电子不再是孤对电子。
