硫铝桥键稳定平面CAl4结构的理论研究

doi:10.7503/cjcu20180480

摘要/Abstract

摘要：

在B3LYP/def2-TZVP水平下, 利用硫铝桥连平面CAl₄结构, 设计了含平面四配位碳的单硫桥连CAl₄S^-和具有准平面四配位碳的四硫桥连CAl₄S₄结构. 团簇搜索结果表明两团簇均为势能面的极小值点, 并且两团簇均具有双重芳香性(σ+π). 单硫桥连CAl₄S得失电子的稳定性研究结果表明, CAl₄S^-为不同价态下的能量最低点, 说明其热力学和动力学稳定性最好, 证明其在实验中被捕获的可能性极大. 准平面结构CAl₄S₄的适应性自然密度划分(AdNDP)分析表明, 其稳定性主要来源于价电子的离域, 其中三中心二电子σ键维持Al-S骨架的稳定, 五中心二电子σ键维持C-Al核心的稳定, 五中心二电子π键有利于整个准平面的整体稳定性.

关键词: 平面碳, 四配位碳, 芳香性, 密度泛函理论, 化学键

Abstract:

Two planar tetracoordinate carbon(pTC) derivatives, planar CAl₄S^- and quasi-planar CAl₄S₄, were investigated to stabilize the planar CAl₄ core. It was indicated that through structural searches at the B3LYP/def2-TZVP level both of the proposed clusters by the Al-S bridge were global minima of potential energy surface with double aromaticity(σ+π). The planar CAl₄S^- was likely to be captured in the experiment due to its thermodynamic stability. The adaptive natural density partitioning(AdNDP) analysis of quasi-planar CAl₄S₄ suggests that its stability was mainly contributed by partial delocalization of electrons. Four 3-center 2-electron σ-bonds maintain the stability of the Al-S framework; three 5-center 2-electron σ-bonds maintain the stability of the C-Al core; one 5-center 2-electron π-bond facilitates the integral stability of the entire quasiplane.

Key words: Planar carbon, Tetracoordinate carbon, Aromaticity, Density functional theory, Chemical bonding

中图分类号:

O641

TrendMD:

张醒醒, 王艺桥, 耿允, 张珉, 苏忠民. 硫铝桥键稳定平面CAl₄结构的理论研究. 高等学校化学学报, 2018, 39(11): 2485.

ZHANG Xingxing, WANG Yiqiao, GENG Yun, ZHANG Min, SU Zhongmin. Theoretical Studies on Enhancing the Stability of the Planar CAl₄ by Al-S Bridge^†. Chem. J. Chinese Universities, 2018, 39(11): 2485.

图/表 11

Fig.1 Low-energy isomers of CAl4S- at B3LYP/def2-TZVP level, together with their relative energy(kJ/mol) difference including zero-point energy(ZPE) corrections

Fig.2 Relative energies of CAl4Sn(n= 0, ±1, -2) isomers at B3LYP/def2-TZVP level

Table 1 Important bonding lengths(nm) of S-01 using different methods

Method	R_C-Al1	R_C-Al2	R_C-Al3	R_C-Al4	R_S-Al2	R_S-Al4	R_Al1-Al2	R_Al1-Al3	R_Al2-Al4	R_Al3-Al4
B3LYP	0.195	0.197	0.202	0.198	0.226	0.227	0.292	0.285	0.271	0.268
BPE0	0.194	0.192	0.203	0.197	0.224	0.226	0.305	0.276	0.266	0.263
M06-2X	0.193	0.192	0.205	0.200	0.222	0.228	0.308	0.276	0.266	0.260
CCSD	0.194	0.193	0.203	0.202	0.222	0.229	0.296	0.287	0.268	0.265

Fig.3 Important MOs(α-spin) of S-01(A) and S-02(B) isomers at B3LYP/def2-TZVP level

Table 2 NPA charges(Q) and Wiberg bond indices(WBI) in S-01 and S-02

Structure	Q_C/e	Q_Al/e	Q_S/e	WBI_C-Al	WBI_S-Al
S-01	-1.289	0.238/0.682/0.211/0.580	-0.422	0.135/0.156/0.132/0.145	0.214/0.202
S-02	-1.356	0.405/0.729/0.274/0.405	-0.457	0.121/0.168/0.115/0.121	0.406

Fig.4 AdNDP analyses for the planar S-01 isomerON means occupation numbers.

Fig.5 Optimized geometries of CAl4Sn4(n=0, 1, 2) and their important bond lengths(nm)

Table 3 NPA charges, Wiberg bond indices(WBI) and Nucleus-independent chemical shift(NICS)

Cluster	Q_C/e	Q_Al/e	Q_S/e	WBI_C-Al	WBI_S-Al	WBI_{Al -Al}	WBI_C	WBI_Al	WBI_S	NICS_d(1)	NICS_u(1)
CAl₄S₄	-2.48	1.47	-0.85	0.55	0.83	0.09	2.46	2.43	1.84	-14.01	-21.96
CAl₄ $S 4 +$	-0.63	0.73	-0.33	0.00	0.23	0.02	0.58	0.61	0.53	-12.17	-6.94
CAl₄ $S 4 2 +$	-1.84	1.53	-0.57	0.42	0.87	0.23	2.41	2.32	2.22	-13.60	-16.11

Table 3 NPA charges, Wiberg bond indices(WBI) and Nucleus-independent chemical shift(NICS)

Cluster	Q_C/e	Q_Al/e	Q_S/e	WBI_C-Al	WBI_S-Al	WBI_{Al -Al}	WBI_C	WBI_Al	WBI_S	NICS_d(1)	NICS_u(1)
CAl₄S₄	-2.48	1.47	-0.85	0.55	0.83	0.09	2.46	2.43	1.84	-14.01	-21.96
CAl₄ $S 4 +$	-0.63	0.73	-0.33	0.00	0.23	0.02	0.58	0.61	0.53	-12.17	-6.94
CAl₄ $S 4 2 +$	-1.84	1.53	-0.57	0.42	0.87	0.23	2.41	2.32	2.22	-13.60	-16.11

Fig.6 Low-energy isomers of CAl4S4 at B3LYP/def2-TZVP level, together with their relative energy(kJ/mol) difference including zero-point energy(ZPE) corrections

Fig.7 AdNDP orbitals of the quasi-planar C4v P-01(A) and their corresponding important MOs(B)

Table 4 Percentage from three elements to the MOs of quasi-planar P-01

MO	Percentage(%)			MO	Percentage(%)
MO	C	Al	S	MO	C	Al	S
HOMO	43.04	19.84	37.12	HOMO-10	3.53	30.63	65.84
HOMO-1	24.97	20.19	54.84	HOMO-11	11.82	25.42	62.76
HOMO-2	24.97	20.19	54.84	HOMO-12	0.03	46.21	53.76
HOMO-3	0.02	9.10	90.88	HOMO-13	17.22	45.50	37.28
HOMO-4	3.71	20.09	76.20	HOMO-14	17.22	45.50	37.28
HOMO-5	3.71	20.09	76.20	HOMO-15	41.06	35.50	23.44
HOMO-6	0	21.08	78.92	HOMO-16	0.11	13.73	86.16
HOMO-7	10.74	32.02	57.24	HOMO-17	0.30	17.34	82.36
HOMO-8	0.40	21.88	77.72	HOMO-18	0.30	17.34	82.36
HOMO-9	3.53	30.63	65.84	HOMO-19	6.69	30.39	62.92

参考文献 38

[1]	Monkhorst H. J., J. Chem. Soc. Chem. Commun., 1968, 18, 1111—1112
[2]	Hoffmann R., Alder R. W., Wilcox C. F. Jr., J. Am. Chem. Soc., 1970, 92, 4992—4993
[3]	Collins J. B., Dill J. D., Jemmis E. D., Apeloig Y., Schleyer P. V. R., Seeger R., Pople J. A., J. Am. Chem. Soc., 1976, 98, 5419—5427
[4]	Wang Z. X., Schleyer P. V. R., J. Am. Chem. Soc., 2001, 123, 994—995
[5]	Thommen M., Keese R., Syn. Lett., 1997, 28, 231—240
[6]	Rasmussen D. R., Radom L., Angew. Chem. Int. Ed., 1999, 38, 2876—2878
[7]	Wu Y. B., Li Z. X.,Pu X. H., Wang Z. X., J. Phys. Chem. C, 2011, 115, 3187—13192
[8]	Cui Z. H., Shao C. B., Gao S. M., Ding Y. H., Phys. Chem. Chem. Phys., 2010, 12, 13637—13645
[9]	Cui Z. H., Ding Y. H., Phys. Chem. Chem. Phys., 2011, 13, 5960—5966
[10]	Cui Z. H., Contreras M., Ding Y. H., Merino G., J. Am. Chem. Soc., 2011, 133, 13228—13231
[11]	Averkiev B. B., Zubarev D. Y., Wang L. M., Huang W., Wang L. S., Boldyrev A. I., J. Am. Chem. Soc., 2008, 130, 9248—9250
[12]	Wang L. M., Huang W., Averkiev B. B., Boldyrev A. I., Wang L. S., Angew. Chem. Int. Ed., 2007, 46, 4550—4553
[13]	Averkiev B. B., Wang L. M., Huang W., Wang L. S., Boldyrev A. I., Phys. Chem. Chem. Phys., 2009, 11, 9840—9849
[14]	Gao S. M., He H. P., Ding Y. H., Chem. J. Chinese Universities, 2012, 33(12), 2739—2745
	(高斯萌, 贺海鹏, 丁益宏. 高等学校化学学报, 2012, 33(12), 2739—2745)
[15]	Gao S. M., He H. P., Ding Y. H., Chem. J. Chinese Universities, 2013, 34(1), 185—191
	(高斯萌, 贺海鹏, 丁益宏. 高等学校化学学报, 2013, 34(1), 185—191)
[16]	Minkin V. I., Minyaev R. M., Zakharov I. I., J. Chem. Soc. Chem. Commun., 1977, 7, 213—214
[17]	Minyaev R. M., Gribanova T. N., Russ. Chem. Bull., 2000, 49, 783—793
[18]	Wiberg K. B., Chem. Rev., 1989, 89, 975—983
[19]	Gunale A., Pritzkow H., Siebert W., Steiner D., Berndt A., Angew. Chem. Int. Ed., 1995, 34, 1111—1113
[20]	Minyaev R. M., Minkin V. I., Gribanova T. N., Starikov A. G., Hoffmann R., J. Org. Chem., 2003, 68, 8588—8594
[21]	Höltzl T., Janssens E., Veldeman N., Veszpremi T., Lievens P., Nguyen M. T., Chem. Phys. Chem., 2008, 9, 833—838
[22]	Schollenberger M., Nuber B., Ziegler M. L., Angew. Chem. Int. Ed., 1992, 31, 350—351
[23]	Ruck M., Angew. Chem. Int. Ed., 1997, 36, 1971—1973
[24]	Lein M., Frunzke J., Frenking G., Angew. Chem. Int. Ed, 2003, 42, 1303—1306
[25]	Islas R., Heine T Ito K., Schleyer P. V. R., Merino G., J. Am. Chem. Soc., 2007, 129, 14767—14774
[26]	Cotton F. A., Millar M., J. Am. Chem. Soc., 1977, 99, 7886—7891
[27]	Radom L., Rasmussen D. R., Pure Appl. Chem., 1998, 70, 1977—1984
[28]	Rao V. B., George C. F., Wolff S., Agosta W. C., J. Am. Chem. Soc., 1985, 107, 5732—5739
[29]	Mcgrath M. P., Radom L., J. Am. Chem. Soc., 1993, 115, 3320—3321
[30]	Lyons J. E., Rasmussen D. R., Mcgrath M. P., Nobes R. H., Radom L., Angew. Chem. Int. Ed., 1994, 33, 1667—1668
[31]	Schleyer P. V. R., Boldyrev A. I., J. Chem. Soc. Chem. Commun., 1991, 21, 1536—1538
[32]	Boldyrev A. I., Simons J., J. Am. Chem. Soc., 1998, 120, 7967—7972
[33]	Li X., Wang L. S., Boldyrev A. I, Simon J., J. Am. Chem. Soc., 1999, 121, 6033—6038
[34]	Boldyrev A. I., Li X., Wang L. S., Geske G. D., Boldyrev A. I., Angew. Chem. Int. Ed., 2000, 39, 3307—3310
[35]	Wang L. S., Boldyrev A. I., Li X., Simon J., J. Am. Chem. Soc., 2000, 122, 7681—7687
[36]	Li Y., Liao Y., Schleyer P. V. R., Chen Z., Nanoscale, 2014, 6, 10784—10791
[37]	Xu J., Zhang X. X., Yu S., Ding Y. H., Bowen K. H., J. Phy. Chem. Lett., 2017, 8, 2263—2267
[38]	Frisch M. J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A. F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Montgomery J. A. Jr., Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Rega N., Millam N. J., Klene M., Knox J. E., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Martin R. L., Morokuma K., Zakrzewski V. G., Voth G. A., Salvador P., Dannenberg J. J., Dapprich S., Daniels A. D., Farkas Ö., Foresman J. B., Ortiz J. V., Cioslowski J., Fox D. J., Gaussian 09, Revision A.1, Gaussian Inc., Wallingford CT, 2009

相关文章 15

[1]	何鸿锐, 夏文生, 张庆红, 万惠霖. 羟基氧化铟团簇与二氧化碳和甲烷作用的密度泛函理论研究[J]. 高等学校化学学报, 2022, 43(8): 20220196.
[2]	黄汉浩, 卢湫阳, 孙明子, 黄勃龙. 石墨炔原子催化剂的崭新道路:基于自验证机器学习方法的筛选策略[J]. 高等学校化学学报, 2022, 43(5): 20220042.
[3]	郭谨昌, 刘芳林. 平面五配位硅、锗XBe₅H₆(X=Si, Ge)团簇[J]. 高等学校化学学报, 2022, 43(4): 20210807.
[4]	刘洋, 李旺昌, 张竹霞, 王芳, 杨文静, 郭臻, 崔鹏. Sc₃C₂@C₈₀与[12]CPP纳米环之间非共价相互作用的理论研究[J]. 高等学校化学学报, 2022, 43(11): 20220457.
[5]	王园月, 安梭梭, 郑旭明, 赵彦英. 5-巯基-1, 3, 4-噻二唑-2-硫酮微溶剂团簇的光谱和理论计算研究[J]. 高等学校化学学报, 2022, 43(10): 20220354.
[6]	周成思, 赵远进, 韩美晨, 杨霞, 刘晨光, 贺爱华. 硅烷类外给电子体对丙烯-丁烯序贯聚合的调控作用[J]. 高等学校化学学报, 2022, 43(10): 20220290.
[7]	程媛媛, 郗碧莹. ·OH自由基引发CH₃SSC $H 3 •$ ⁺自由基裂解反应机理的理论研究[J]. 高等学校化学学报, 2022, 43(10): 20220271.
[8]	黄罗仪, 翁约约, 黄旭慧, 王朝杰. 车前草中黄酮类成分结构和性质的理论研究[J]. 高等学校化学学报, 2021, 42(9): 2752.
[9]	钟声广, 夏文生, 张庆红, 万惠霖. 电中性团簇MCu₂O_x(M=Cu²⁺, Ce⁴⁺, Zr⁴⁺)上甲烷和二氧化碳直接合成乙酸的理论研究[J]. 高等学校化学学报, 2021, 42(9): 2878.
[10]	马丽娟, 高升启, 荣祎斐, 贾建峰, 武海顺. Sc, Ti, V修饰B/N掺杂单缺陷石墨烯的储氢研究[J]. 高等学校化学学报, 2021, 42(9): 2842.
[11]	刘昌辉, 梁国俊, 李妍璐, 程秀凤, 赵显. NH₃在硼纳米管表面吸附的密度泛函理论研究[J]. 高等学校化学学报, 2021, 42(7): 2263.
[12]	应富鸣, 计辰儒, 苏培峰, 吴玮. 基于完全活性空间自洽场的杂化多组态密度泛函方法λ-DFCAS[J]. 高等学校化学学报, 2021, 42(7): 2218.
[13]	郑若昕, 张颖, 徐昕. 低标度XYG3双杂化密度泛函的开发与测评[J]. 高等学校化学学报, 2021, 42(7): 2210.
[14]	王建, 张红星. 四配位铂磷光发射体结构与光物理性质关系的理论研究[J]. 高等学校化学学报, 2021, 42(7): 2245.
[15]	胡伟, 刘小峰, 李震宇, 杨金龙. 金刚石纳米线氮空位色心的表面与尺寸效应[J]. 高等学校化学学报, 2021, 42(7): 2178.

硫铝桥键稳定平面CAl₄结构的理论研究

Theoretical Studies on Enhancing the Stability of the Planar CAl₄ by Al-S Bridge^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 38

相关文章 15

编辑推荐

Metrics

本文评价