[MAl5]+(M=Si,Ge,Sn,Pb)体系结构和稳定性的理论研究

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (4): 772.

[MAl₅]⁺(M=Si,Ge,Sn,Pb)体系结构和稳定性的理论研究

贺海鹏, 崔中华, 丁益宏

吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春 130023

收稿日期:2009-07-20 出版日期:2010-04-10 发布日期:2010-04-10
通讯作者: 丁益宏, 男, 博士, 教授, 博士生导师, 主要从事量子化学理论研究. E-mail: yhdd@mail.jlu.edu.cn
基金资助:
国家自然科学基金(批准号: 20103003, 20573046, 20773054)和吉林省杰出青年基金(批准号: 20050103)、新世纪优秀人才支持计划(NCET)和教育部博士点基金(批准号: 20070183028)资助项目.

Theoretical Studies on the Structures and Stabilities of [MAl₅]⁺(M=Si,Ge,Sn,Pb)

HE Hai-Peng, CUI Zhong-Hua, DING Yi-Hong*

State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China

Received:2009-07-20 Online:2010-04-10 Published:2010-04-10
Contact: DING Yi-Hong. E-mail: yhdd@mail.jlu.edu.cn
Supported by:
国家自然科学基金(批准号: 20103003, 20573046, 20773054)和吉林省杰出青年基金(批准号: 20050103)、新世纪优秀人才支持计划(NCET)和教育部博士点基金(批准号: 20070183028)资助项目.

摘要/Abstract

摘要：

利用B3LYP和CCSD(T)(单点)方法, 研究了含Si, Ge, Sn, Pb的六原子体系[MAl₅]⁺中各个异构体的结构及稳定性. 研究结果表明, 尽管与[CAl₅]⁺一样也具有18个价电子, 但[MAl₅]⁺(M=Si, Ge, Sn, Pb)体系并不存在具有平面五配位结构的异构体, 其能量的全局极小点为具有C_s对称性的蝶形异构体Int1, 这是由于中心原子M(Si, Ge, Sn, Pb)较大的体积显著破坏了[MAl₅]⁺中平面五配位结构的稳定性所致.

关键词: [MAl5]+(M=Si, Ge, Sn, Pd); 平面五配位; 异构体; 热力学稳定性

Abstract:

By means of the B3LYP and CCSD(T)(single-point) methods, we investigated the isomeric structures and thermodynamic stabilities of four hexa-atomic systems [MAl₅]⁺(M=Si,Ge,Sn,Pb). The results show that although bearing the same 18-valence electrons as [CAl₅]⁺, all the [MAl₅]⁺(M=Si, Ge, Sn, Pb) systems do not have a planar pentacoordinate M isomer. Instead, the global structure is a C_s-symmetrized butterfly isomer Int1. This can be rationalized that the bulkier central atom M(Si, Ge, Sn, Pb) than C has significantly destructed the stability of the planar pentacoordinate structure of [MAl₅]⁺.

Key words: [MAl5]+(M=Si, Ge, Sn, Pd); Planar pentacoordinate; Isomer; Thermodynamic stability

TrendMD:

贺海鹏, 崔中华, 丁益宏. [MAl₅]⁺(M=Si,Ge,Sn,Pb)体系结构和稳定性的理论研究. 高等学校化学学报, 2010, 31(4): 772.

HE Hai-Peng, CUI Zhong-Hua, DING Yi-Hong*. Theoretical Studies on the Structures and Stabilities of [MAl₅]⁺(M=Si,Ge,Sn,Pb). Chem. J. Chinese Universities, 2010, 31(4): 772.

参考文献

[1]Hoffmann R., Alder R. W., Wilcox C. F.. J. Am. Chem. Soc.[J], 1970, 92: 4992—4993
[2]Hoffmann R.. Pure. Appl. Chem.[J], 1971, 28: 181—194
[3]Sorger K., Schleyer P. v. R.. J. Mol. Struct.[J], 1995, 338: 317—346
[4]Rottger D., Erker G.. Angew. Chem. Int. Ed.[J], 1997, 36: 812—827
[5]Choukroun R., Cassoux P.. Acc. Chem. Res.[J], 1999, 32: 494—502
[6]Siebert W., Gunale A.. Chem. Soc. Rev.[J], 1999, 28: 367—371
[7]Wu Y. B., Lu H. G., Li S. D., et al.. J. Phys. Chem. A[J], 2009, 113: 3395—3402
[8]Li X., Wang L. S., Boldyrev A. I., et al.. J. Am. Chem. Soc.[J], 1999, 121: 6033—6038
[9]Wang L. S., Boldyrev A. I., Li X., et al.. J. Am. Chem. Soc.[J], 2000, 122: 7681—7687
[10]L. X., Zhang H. F.., Wang L. S., et al.. Angew. Chem. Int. Ed.[J], 2000, 39: 3630—3632
[11]Merino G., Mendez-Rojas M. A., Vela A.. J. Am. Chem. Soc.[J], 2003, 125: 6026—6027
[12]Pancharatna P. D., Mendez-Rojas M. A., Merino G., et al.. J. Am. Chem. Soc.[J], 2004, 126: 15309—15315
[13]Perez N., Heine T., Barthel R., et al.. Org. Lett.[J], 2005, 7: 1509—1512
[14]Balzani V., Credi A., Raymo F. M., et al.. Angew. Chem. Int. Ed.[J], 2000, 39: 3348—3352
[15]Stoddart J. F.. Acc. Chem. Res.[J], 2001, 34: 409—522
[16]Thomas O. C., Zheng W. J., Bowen K. H.. J. Chem. Phys.[J], 2001, 114: 5514—5519
[17]Exner K., Schleyer P. v. R.. Science[J], 2000, 290: 1937—1940
[18]Wang Z. X., Schleyer P. v. R.. Science[J] 2001, 292: 2465—2469
[19]Boldyrev A. I., Wang L. S.. J. Phys. Chem. A[J], 2001, 105: 10759—10775
[20]Wang L. M., Huang W., Averkiev B. B., et al.. Angew. Chem. Int. Ed.[J], 2007, 46: 4550—4553
[21]Averkiev B. B., Zubarev D. Y., Wang L. M., et al.. J. Am. Chem. Soc.[J], 2008, 130: 9248—9250
[22]Schleyer P. v. R., Boldyrev A. I.. J. Chem. Soc. Chem. Commun.[J], 1991: 1536—1538
[23]Boldyrev A. I., Li X., Wang L. S.. Angew. Chem. Int. Ed.[J], 2000, 39: 3307—3310
[24]Pei Y., An W., Ito K., et al.. J. Am. Chem. Soc.[J], 2008, 130: 10394—10400
[25]Frisch M. J., Trucks G. W., Schlegel H. B., et al.. Gaussian 03, Revision D.02[CP], Wallingford CT: Gaussian Inc., 2004
[26]Ennington R. Ⅱ, Todd K., Millam J., et al.. R., GaussView, Version 3.09[CP], Shawnee Mission KS: Semichem. Inc., 2003
[27]Schaftenaar G.. MOLDEN3.4[CP], The Netherlands: CAOS/CAMM Center, 1998

[MAl₅]⁺(M=Si,Ge,Sn,Pb)体系结构和稳定性的理论研究

Theoretical Studies on the Structures and Stabilities of [MAl₅]⁺(M=Si,Ge,Sn,Pb)

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 0

编辑推荐

Metrics

本文评价