Dong Xue, Liu Yu-Qian, Liu Xin-Bo, Pan Sudip, Cui Zhong-Hua, Merino Gabriel
Institute of Atomic and Molecular Physics, Jilin University, Changchun, 130023, China.
Fachbereich Chemie, Philipps-Universitt Marburg, Hans-Meerwein-Straße, 35043, Marburg, Germany.
Angew Chem Int Ed Engl. 2022 Oct 17;61(42):e202208152. doi: 10.1002/anie.202208152. Epub 2022 Sep 16.
A new class of beryllium-boron clusters, beryllo-borospherene, is described herein theoretically. When beryllium is gradually added to the B motif, it undergoes drastic structural modifications. The global minimum of the Be B cluster is an Archimedean beryllo-borospherene in a A electronic ground state, composed of four boron triangles linked at each corner, resulting in a truncated tetrahedron with four B rings capped with four beryllium atoms. Beryllium forms strong bonding with the boron clusters through strong electrostatic and covalent interactions. For instance, the bonding between a beryllium atom and Be B unit is best described as a Be fragment in a P excited state forming a strong and polarized electron-sharing bond with Be B , followed by several dative interactions by employing its vacant s, p, and very high-lying d orbitals. Counterintuitively, for an s-block element, the p orbitals of beryllium are the most crucial atomic orbitals for bonding rather than s orbitals.
本文从理论上描述了一类新型的铍硼团簇——铍硼球烯。当铍逐渐添加到硼结构单元中时，会发生剧烈的结构变化。Be₄B₄团簇的全局最小值是处于¹A电子基态的阿基米德铍硼球烯，它由四个在每个角相连的硼三角形组成，形成一个截顶四面体，其中四个B环由四个铍原子封顶。铍通过强烈的静电和共价相互作用与硼团簇形成强键。例如，铍原子与Be₄B₄单元之间的键合最好描述为处于³P激发态的Be片段与Be₄B₄形成强且极化的电子共享键，随后通过利用其空的s、p和非常高能量的d轨道进行若干配位相互作用。与直觉相反，对于一个s区元素，铍的p轨道是键合中最关键的原子轨道，而不是s轨道。
