平面四配位和五配位的B6S5团簇

doi:10.7503/cjcu20200106

摘要/Abstract

摘要：

采用B3LYP/def2-TZVP优化和在耦合簇方法(CCSD)单点水平下, 将$B_{6}S^{n}_{5}$ (n=0, +1, +2)作为基础结构研究证实了S原子对于形成B平面多配位结构具有良好的作用. 研究发现, $B_{6}S^{n}_{5}$ (n=0, +1, +2) 3种价态下最稳定和次稳定结构均为纯平面结构, 仅在不同电子数下两者的能量次序发生改变. 中性的B₆S₅因满足18电子规则其最稳定结构具有D₅_h对称性, 且中心B为平面五配位. 在$B_{6}S^{+}_{5}$和$B_{6}S^{2+}_{5}$中, 其17电子和16电子时的最稳定结构中的所有B均为平面四配位. 18电子的B₆S₅更为稳定.

关键词: $B_{6}S^{n}_{5}$ (n=0,+1+2), 平面四配位, 平面五配位, 芳香性, 硫桥连

Abstract:

At the level of B3LYP/def2-TZVP optimization and CCSD single point energy, $B_{6}S^{n}_{5}$ (n=0, +1, +2) was utilized to validate the valuable effect of peripheral sulfur atom on constructing planar coordinated boron. The structures of global energy minimum(GEM) and the second lowest energy minimum in three charge states are purely planar ones, and their structures are very similar. Only their order is exchanged with the loss of the electrons. There exists a planar pentacoordinate boron in the GEM structure of D₅_h-B₆S₅ due to the 18 electron rule, and there are all the planar tetracoordinate borons in the GEM structure of $B_{6}S^{n}_{5}$ (n=0, +1, +2). Meanwhile, the sulfur-bridging bonding is another key factor to maintain their planar molecular structures.

Key words: $B_{6}S^{n}_{5}$ (n=0,+1+2), Planar tetracoordinate, Planar pentacoordinate, Aromaticity, Sulfur bridge

中图分类号:

O641

TrendMD:

王艺桥,王聪,刘兴满,张珉,耿允,赵亮. 平面四配位和五配位的B₆S₅团簇. 高等学校化学学报, 2020, 41(7): 1625.

WANG Yiqiao,WANG Cong,LIU Xingman,ZHANG Min,GENG Yun,ZHAO Liang. Planar Tetracoordinate Boron and Pentacoordinate Boron in B₆S₅ Clusters^†. Chem. J. Chinese Universities, 2020, 41(7): 1625.

图/表 6

Fig.1 Important optimized structures at the B3LYP/def2-TZVP level for B6Sn5(n=0, +1, +2) with their important bond distances(nm) Relative energies(kJ/mol) calculated at the single-point CCSD/6-31G(d) level including zero-point energy(ZPE) corrections at B3LYP/def2-TZVP.

Table 1 NPA charges(Q) of B and S atoms and interatomic Wiberg bond index(WBI) of the ppB structures 1—3 of B6Sn5(n=0, +1, +2) clusters based on B3LYP/def2-TZVP results

Structure	Q_Bc/e	Q_Bm/e	Q_S/e	WBI_Bc—Bm	WBI_Bm—Bm	WBI_Bm—S	WBI_Bc—S
1	-1.22	0.18	0.07	0.66	0.28	1.12	0.09
2	-0.77	0.11	0.24	0.62	0.26	1.20	0.05
3	-0.23	0.03	0.41	0.60	0.25	1.25	0.02

Table 2 Calculated vertical electron affinity(VEA), vertical detachment energy(VDE), adiabatic electron affinity(AEA), adiabatic detachment energy(ADE), nucleus-independent chemical shift(NICS) of the ppB structures 1—3

Structure	VEA/eV	VDE/eV	AEA/eV	ADE/eV	NICS(1)	NICS(2)
1	-0.55	7.60	-1.13	7.43	-16.98	-3.31
2	-7.25	12.82	-7.43	12.20	-14.40	-2.76
3	-12.10	18.44	-12.20	17.79	-11.24	-2.45

Fig.2 Important AdNDP orbitals of ppB-B6S5(structure 1) and their occupation numbers(ONs)

Fig.3 Important AdNDP orbitals of ptB-B6S52+(structure 6) and their occupation numbers(ONs)

Table 3 Important B3LYP/def2-TZVP results of the ptB structures 4—6 of B6Sn5(n=0, +1, +2) clusters, including the Q of B and S atoms and interatomic WBI(different values from different atoms due to C2v symmetry)

Structure	Q_Bc/e	Q_Bm/e	Q_S/e	WBI_Bc—Bc	WBI_Bc—Bm	WBI_Bm—S
4	-0.26	-0.05/0.04	0.04/0.14/0.11	1.26	0.62/0.63	1.13/1.09
5	0.07	-0.04/0.01	0.30/0.45/0.47	1.10	0.54/0.59	1.21/1.19
6	0.01	-0.06/-0.03	0.14/0.15/0.23	0.96	0.57/0.58	1.27/1.25

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平面四配位和五配位的B₆S₅团簇

Planar Tetracoordinate Boron and Pentacoordinate Boron in B₆S₅ Clusters^†

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