Dong Xue, Tiznado William, Liu Yu-Qian, Leyva-Parra Luis, Liu Xin-Bo, Pan Sudip, Merino Gabriel, Cui Zhong-Hua
Institute of Atomic and Molecular Physics, Jilin University, Changchun, 130023, China.
Universidad Andrés Bello, Facultad de Ciencias Exactas, Departamento de Ciencias Químicas, Centro de Química Teórica & Computacional (CQT&C), Avenida República 275, 8370146, Santiago de Chile, Chile.
Angew Chem Int Ed Engl. 2023 Aug 1;62(31):e202304997. doi: 10.1002/anie.202304997. Epub 2023 Jun 26.
Planar boron clusters have often been regarded as "π-analogous" to aromatic arenes because of their similar delocalized π-bonding. However, unlike arenes such as C H and C H , boron clusters have not previously shown the ability to form sandwich complexes. In this study, we present the first sandwich complex involving beryllium and boron, B Be B . The global minimum of this combination adopts a unique architecture having a D geometry, featuring an unprecedented monocyclic Be ring sandwiched between two quasi-planar B motifs. The thermochemical and kinetic stability of B Be B can be attributed to strong electrostatic and covalent interactions between the fragments. Chemical bonding analysis shows that B Be B can be considered as a [B ] [Be ] [B ] complex. Moreover, there is a significant electron delocalization within this cluster, supported by the local diatropic contributions of the B and Be fragments.
平面硼簇由于其类似的离域π键合作用，常常被认为与芳香芳烃“π类似”。然而，与诸如C₆H₆和C₁₀H₈等芳烃不同，硼簇此前尚未表现出形成夹心配合物的能力。在本研究中，我们展示了首个涉及铍和硼的夹心配合物，即B₂BeB₂。这种组合的全局最小值采用了具有D₂h几何结构的独特架构，其特征是一个前所未有的单环铍环夹在两个准平面硼基序之间。B₂BeB₂的热化学和动力学稳定性可归因于各片段之间强烈的静电和共价相互作用。化学键分析表明，B₂BeB₂可被视为一种[B₂]²⁻[Be]²⁺[B₂]²⁻配合物。此外，在该簇内存在显著的电子离域，这得到了硼和铍片段的局部抗磁贡献的支持。
