Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.
Department of Chemistry, Xinzhou Teachers' University, Xinzhou 034000, China.
Molecules. 2023 May 5;28(9):3892. doi: 10.3390/molecules28093892.
Transition-metal-doped boron nanoclusters exhibit unique structures and bonding in chemistry. Using the experimentally observed seashell-like borospherenes B and B as ligands and based on extensive first-principles theory calculations, we predict herein a series of novel transition-metal-centered endohedral seashell-like metallo-borospherenes Sc@B (), Ti@B (), V@B (), and V@B () which, as the global minima of the complex systems, turn out to be the boron analogues of dibenzenechromium Cr(CH) with two B ligands on the top and bottom interconnected by four or five corner boron atoms on the waist and one transition-metal "pearl" sandwiched at the center in between. Detailed molecular orbital, adaptive natural density partitioning (AdNDP), and iso-chemical shielding surface (ICSS) analyses indicate that, similar to Cr(CH), these endohedral seashell-like complexes follow the 18-electron rule in bonding patterns (1S1P1D), rendering spherical aromaticity and extra stability to the systems.
过渡金属掺杂硼纳米团簇在化学中表现出独特的结构和键合。本文以实验观察到的贝壳状硼球烯 B 和 B 作为配体，并基于广泛的第一性原理理论计算，预测了一系列新型的以过渡金属为中心的夹心贝壳状金属硼球烯 Sc@B (), Ti@B (), V@B (), 和 V@B ()，作为复杂体系的全局最小值，它们是二苯铬 Cr(CH)的硼类似物，顶部和底部各有两个 B 配体，腰部通过四个或五个顶角硼原子相互连接，中心夹有一个过渡金属“珍珠”。详细的分子轨道、自适应自然密度分区（AdNDP）和等化学屏蔽表面（ICSS）分析表明，与 Cr(CH) 类似，这些夹心贝壳状配合物遵循 18 电子规则的成键模式 (1S1P1D)，赋予体系球形芳香性和额外的稳定性。
