Planar Tetracoordinate Boron and Pentacoordinate Boron in B6S5 Clusters†

doi:10.7503/cjcu20200106

Abstract

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

CLC Number:

O641

TrendMD:

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

Figures/Tables 6

References 48

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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

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

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

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

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

Planar Tetracoordinate Boron and Pentacoordinate Boron in B₆S₅ Clusters^†

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