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

doi:10.7503/cjcu20180480

Abstract

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

CLC Number:

O641

TrendMD:

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

Figures/Tables 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

References 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

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

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 11

References 38

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	HE Hongrui, XIA Wensheng, ZHANG Qinghong, WAN Huilin. Density-functional Theoretical Study on the Interaction of Indium Oxyhydroxide Clusters with Carbon Dioxide and Methane [J]. Chem. J. Chinese Universities, 2022, 43(8): 20220196.
[2]	WONG Honho, LU Qiuyang, SUN Mingzi, HUANG Bolong. Rational Design of Graphdiyne-based Atomic Electrocatalysts： DFT and Self-validated Machine Learning [J]. Chem. J. Chinese Universities, 2022, 43(5): 20220042.
[3]	GUO Jinchang, LIU Fanglin. Planar Pentacoordinate Silicon and Germanium in XBe₅H₆（X=Si， Ge） Clusters [J]. Chem. J. Chinese Universities, 2022, 43(4): 20210807.
[4]	LIU Yang, LI Wangchang, ZHANG Zhuxia, WANG Fang, YANG Wenjing, GUO Zhen, CUI Peng. Theoretical Exploration of Noncovalent Interactions Between Sc₃C₂@C₈₀ and ［12］Cycloparaphenylene Nanoring [J]. Chem. J. Chinese Universities, 2022, 43(11): 20220457.
[5]	ZHOU Chengsi, ZHAO Yuanjin, HAN Meichen, YANG Xia, LIU Chenguang, HE Aihua. Regulation of Silanes as External Electron Donors on Propylene/butene Sequential Polymerization [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220290.
[6]	WANG Yuanyue, AN Suosuo, ZHENG Xuming, ZHAO Yanying. Spectroscopic and Theoretical Studies on 5-Mercapto-1，3，4-thiadiazole-2-thione Microsolvation Clusters [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220354.
[7]	CHENG Yuanyuan, XI Biying. Theoretical Study on the Fragmentation Mechanism of CH₃SSCH₃ Radical Cation Initiated by OH Radical [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220271.
[8]	MA Lijuan, GAO Shengqi, RONG Yifei, JIA Jianfeng, WU Haishun. Theoretical Investigation of Hydrogen Storage Properties of Sc， Ti， V-decorated and B/N-doped Monovacancy Graphene [J]. Chem. J. Chinese Universities, 2021, 42(9): 2842.
[9]	ZHONG Shengguang, XIA Wensheng, ZHANG Qinghong, WAN Huilin. Theoretical Study on Direct Conversion of CH₄ and CO₂ into Acetic Acid over MCu₂O_x（M = Cu²⁺， Ce⁴⁺， Zr⁴⁺） Clusters [J]. Chem. J. Chinese Universities, 2021, 42(9): 2878.
[10]	HUANG Luoyi, WENG Yueyue, HUANG Xuhui, WANG Chaojie. Theoretical Study on the Structures and Properties of Flavonoids in Plantain [J]. Chem. J. Chinese Universities, 2021, 42(9): 2752.
[11]	WANG Jian, ZHANG Hongxing. Theoretical Study on the Structural-photophysical Relationships of Tetra-Pt Phosphorescent Emitters [J]. Chem. J. Chinese Universities, 2021, 42(7): 2245.
[12]	HU Wei, LIU Xiaofeng, LI Zhenyu, YANG Jinlong. Surface and Size Effects of Nitrogen-vacancy Centers in Diamond Nanowires [J]. Chem. J. Chinese Universities, 2021, 42(7): 2178.
[13]	YANG Yiying, ZHU Rongxiu, ZHANG Dongju, LIU Chengbu. Theoretical Study on Gold-catalyzed Cyclization of Alkynyl Benzodioxin to 8-Hydroxy-isocoumarin [J]. Chem. J. Chinese Universities, 2021, 42(7): 2299.
[14]	ZHENG Ruoxin, ZHANG Igor Ying, XU Xin. Development and Benchmark of Lower Scaling Doubly Hybrid Density Functional XYG3 [J]. Chem. J. Chinese Universities, 2021, 42(7): 2210.
[15]	LIU Yang, LI Qingbo, SUN Jie, ZHAO Xian. Direct Synthesis of Graphene on AlN Substrates via Ga Remote Catalyzation [J]. Chem. J. Chinese Universities, 2021, 42(7): 2271.