Wang Meng-Hui, Chen Chen, Pan Sudip, Cui Zhong-Hua
Institute of Atomic and Molecular Physics, Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), Jilin University Changchun China
Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University Nanjing China.
Chem Sci. 2021 Oct 26;12(45):15067-15076. doi: 10.1039/d1sc05089c. eCollection 2021 Nov 24.
We report the first planar hexacoordinate gallium (phGa) center in the global minimum of the GaBeAu cluster which has a star-like geometry with A electronic state, possessing a central gallium atom encompassed by a Be hexagon and each Be-Be edge is further capped by an Au atom. The electronic delocalization resulting in double aromaticity (both σ and π) provides electronic stability in the planar form of the GaBeAu cluster. The high kinetic stability of the title cluster is also understood by Born-Oppenheimer molecular dynamics simulations. The energy decomposition analysis in combination with the 'natural orbitals for chemical valence' theory reveals that the bonding in the GaBeAu cluster is best expressed as the doublet Ga atom with 4s4p electronic configuration forming an electron-sharing π bond with the doublet BeAu moiety followed by Ga(s)→[BeAu ] σ-backdonation and two sets of Ga(p)←[BeAu ] σ-donations.
我们报道了GaBeAu团簇全局最小值中的首个平面六配位镓（phGa）中心，该团簇具有星状几何结构和A电子态，其中心镓原子被一个铍六边形包围，且每个铍-铍边进一步被一个金原子覆盖。电子离域导致双重芳香性（σ和π），为GaBeAu团簇的平面形式提供了电子稳定性。通过玻恩-奥本海默分子动力学模拟也理解了标题团簇的高动力学稳定性。结合“化学价自然轨道”理论的能量分解分析表明，GaBeAu团簇中的键合最好表示为具有4s4p电子构型的二重态镓原子与二重态BeAu部分形成一个电子共享π键，随后是Ga(s)→[BeAu]σ-反馈以及两组Ga(p)←[BeAu]σ-给予。
