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, People's Republic of China.
ACS Omega. 2020 Dec 8;5(50):32583-32590. doi: 10.1021/acsomega.0c04876. eCollection 2020 Dec 22.
Nitrogen-based groups are usually not used as ligands to coordinate to the ptC atom. However, here we reported only nitrogen-based ligands to accomplish a theoretically successful square planar C(N) substructure. The first difficulty in accomplishing a square ptC(N) substructure is to conquer the tremendous strain from the planar to tetrahedral arrangements, and the second is to restrict it in a suitable system with the right symmetry. We designed several neutral molecules with the square ptC(N) substructures, and the molecules were studied using the density functional theory method at the B3LYP/6-311++G(3df,3pd) and TPSSh/6-311++G(3df,3pd) level of theory. The results of this work show that the molecules are all real minima on the potential energy surface and successfully achieved the square ptC(N) substructure in the theoretical method. The group orbitals among the square ptC(N) arrangement in the symmetry have been discussed and used to investigate the bonding interactions among all atoms in the square ptC(N) substructure. Usually, the ptC systems have 18 valence electrons, but the present ptC systems mentioned in this work have 24 valence electrons, which is unusual for ptC.
基于氮的基团通常不用作与铂碳（ptC）原子配位的配体。然而，在此我们报道了仅使用基于氮的配体来实现理论上成功的平面正方形碳氮（C(N)）子结构。实现平面正方形铂碳氮（ptC(N)）子结构的第一个困难在于克服从平面构型到四面体构型的巨大张力，第二个困难是将其限制在具有合适对称性的体系中。我们设计了几种具有平面正方形铂碳氮（ptC(N)）子结构的中性分子，并使用密度泛函理论方法在B3LYP/6 - 311++G(3df,3pd)和TPSSh/6 - 311++G(3df,3pd)理论水平下对这些分子进行了研究。这项工作的结果表明，这些分子在势能面上均为真正的极小值，并且在理论方法中成功实现了平面正方形铂碳氮（ptC(N)）子结构。已讨论了D₂ₕ对称性下平面正方形铂碳氮（ptC(N)）排列中的群轨道，并用于研究平面正方形铂碳氮（ptC(N)）子结构中所有原子之间的键相互作用。通常，铂碳（ptC）体系有18个价电子，但本工作中提到的当前铂碳（ptC）体系有24个价电子，这对于铂碳（ptC）来说是不寻常的。
