铬族金属氢化物中M-H 键键能的从头计算

doi:10.6023/A12070460

化学学报 ›› 2012, Vol. 70 ›› Issue (18): 1923-1929.DOI: 10.6023/A12070460 上一篇下一篇

研究论文

铬族金属氢化物中M-H 键键能的从头计算

唐诗雅, 傅尧, 郭庆祥

中国科学技术大学化学系合肥 230026

投稿日期:2012-07-23 发布日期:2012-08-16
通讯作者: 傅尧,郭庆祥
基金资助:
项目受国家自然科学基金(Nos. 20832004, 20972148), 中国科学院(KJCX2-EW-J02)和中央高校基本科研业务费资助. 计算工作在中国科大和上海超算中心完成.

Ab Initio Calculation of M-H Bond Dissociation Energies of Cr-Group Metal Hydrides

Tang Shiya, Fu Yao, Guo Qingxiang

Department of Chemistry, University of Science and Technology of China, Hefei 230026

Received:2012-07-23 Published:2012-08-16
Supported by:
Supporting information for this article is available free of charge via the Internet at http://sioc-journal.cn. Project supported by the National Natural Science Foundation of China (Nos. 20832004, 20972148), Chinese Academy of Science (KJCX2-EW-J02) and the Fundamental Research Funds for the Central Universities. Computations were performed at the Supercomputing Center of USTC and Shanghai.

文章分享

1. 铬族金属氢化物中M-H 键键能的从头计算.PDF(293KB)

摘要/Abstract

铬族金属氢化物M-H 键的均裂是在自由基环化反应中的关键过程, 它直接影响反应的催化效率和选择性. 使用理论方法精确预测铬族金属氢化物M-H 键键能不仅有助于了解这类催化剂的结构与性能关系, 而且对进一步发展高效的自由基环化反应催化剂具有重要的指导意义. 为达此目的, 我们使用不同的理论方法计算14 个有可靠实验值的铬族金属氢化物M-H键键能, 通过比较发现B3P86/lanl2dz+p 方法表现最佳(计算精度为1.6 kcal/mol). 之后我们运用这个理论方法系统地研究了铬族金属氢化物M-H 键键能的构效关系. 就周期性规律而言, 在铬族金属氢化物中, 金属对于M-H 键能的影响大于配体的影响. M-H 键键裂解能的大小顺序为:铬氢络合物<钼氢络合物<钨氢络合物.此外, 我们发现含双茂配体的铬氢化合物中Cr-H 键键能与伸缩振动频率呈良好的线性相关. 有趣的是, 在含双茂配体的铬族金属氢化物中, M-H 键能与键长呈现出良好的正线性相关性. 即“键长越小, 键能越弱”. 通过自然成键轨道分析, 这可能是因为杂化缺失造成原子半径收缩程度比成键变弱引起的扩张程度大.

关键词: 过渡金属氢化物, 键能, 从头算, 杂化缺失

The metal-hydrogen M-H bond homolysis of the Cr-group metal hydrides is a key process in the radical cyclization reactions mediated by these compounds, which directly affects the catalytic efficiency and selectivity of the reactions. Accurate prediction of M-H BDEs (bond dissociation energies) using theoretical methods not only improves our understanding about the structures and properties of the Cr-group metal hydride based catalysts, but also provides important insights into design of new generations of catalysts for radical cyclization reactions. For this purpose, we have calculated the M-H BDEs with different density functional theory methods (including MPW1K, MPW1b95, MPW1PW91, PBE1PBE, B3P86, O3LYP, TPSSH, MPW1KCIS, and TPSS) and compared the theoretical predictions with 14 reliable experimental M-H BDE values recently reported for the Cr-group metal hydrides. It is found that the B3P86/lanl2dz+p method could accurately predict the M-H BDEs with a precision of 1.6 kcal/mol. Using the B3P86/lanl2dz+p method, we next studied the structure-property relationship for the M-H BDEs in Cr-group metal hydrides. As to the periodical trends, we found that the effects of the metals on the M-H BDEs are greater than the effects of the ligands. The M-H BDEs increase in the order:first row metal

Key words: transition-metal hydride, bond dissociation energy, ab initio calculation, hybridization defects

引用此文

唐诗雅, 傅尧, 郭庆祥. 铬族金属氢化物中M-H 键键能的从头计算[J]. 化学学报, 2012, 70(18): 1923-1929.

Tang Shiya, Fu Yao, Guo Qingxiang. Ab Initio Calculation of M-H Bond Dissociation Energies of Cr-Group Metal Hydrides[J]. Acta Chimica Sinica, 2012, 70(18): 1923-1929.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Smith, D. B.; Pulling, M. E.; Norton, J. R. J. Am. Chem. Soc. 2007, 129, 770.

[2] Jasperse, C. P.; Curran, D. P.; Fevig, T. L. Chem. Rev. 1991, 91, 1237.

[3] (a) Choi, J.; Tang, L. H.; Norton, J. R. J. Am. Chem. Soc. 2007, 129, 234;

(b) Tang, L. H.; Papish, E. T.; Abramo, G. P.; Norton, J. R.; Baik, M. H.; Friesner, R. A.; Rappe, A. J. Am. Chem. Soc. 2003, 125, 10093;

(c) Eisenberg, D. C.; Lawrie, C. J. C.; Moody, A. E.; Norton, J. R. J. Am. Chem. Soc. 1991, 113, 4888;

(d) Pleune, B.; Morales, D.; Meunier-Prest, R.; Richard, P.; Collange, E.; Fettinger, J. C.; Poli, R. J. Am. Chem. Soc. 1999, 121, 2209;

(e) Studer, A.; Amrein, S. Synthesis 2002, 7, 835.

[4] O'Connor, J. M.; Friese, S. J. Organometallics 2008, 27, 4280.

[5] Hoff group: (a) Kiss, G.; Zhang, K.; Mukerjee, S. L.; Hoff, C. D. J. Am. Chem. Soc. 1990, 112, 5657;

(b) Lang, R. F.; Ju, T. D.; Kiss, G.; Hoff, C. D.; Bryan, J. C.; Kubas, G. J. J. Am. Chem. Soc. 1994, 116, 7917.

[6] Tilset group : (a) Tilset, M. J. Am. Chem. Soc. 1992, 114, 2740;

(b) Skagestad, V.; Tilset, M. J. Am. Chem. Soc. 1993, 115, 5077;

(c) Tilset, M.; Hamon, J. R.; Hamon, P. Chem. Commun. 1998, 765.

[7] Luo, Y.-R. Comprehensive Handbook of Chemical Bond Energies, 1st ed., CRC Press, 2007.

[8] (a) Qi, X.-J.; Li, Z.; Fu, Y.; Guo, Q.-X.; Liu, L. Organometallics 2008, 27, 2688;

(b) Qi, X.-J.; Fu, Y.; Liu, L.; Guo, Q.-X. Organometallics 2007, 26, 4197;

[9] Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, Jr. J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; 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.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Revision C. 02, Gaussian, Inc., Wallingford CT, 2004.

[10] Zhao, Y.; Schultz, N. E.; Truhlar, D. G. J. Chem. Theory Comput. 2006, 2, 364.

[11] (a) Feng, Y.; Liu, L.; Wang, J.-T.; Huang, H.; Guo, Q.-X. J. Chem. Inf. Comput. Sci. 2003, 43, 2005;

(b) Cheng, Y.-H.; Zhao, X.; Song, K.-S.; Liu, L.; Guo, Q.-X. J. Org. Chem. 2002, 67, 6638;

(c) Song, K.-S.; Liu, L.; Guo, Q.-X. J. Org. Chem. 2003, 68, 262;

(d) Feng, Y.; Liu, L.; Wang, J.-T.; Zhao, S.-W.; Guo, Q.-X. J. Org. Chem. 2004, 69, 3129;

(e) Fu, Y.; Liu, L.; Lin, B.-L.; Mou, Y.; Cheng, Y.-H.; Guo, Q.-X. J. Org. Chem. 2003, 68, 4657

[12] (a) Hoobler, R. J.; Hutton, M. A.; Dillard, M. M.; Castellani, M. P.; Rheingold, A. L.; Rieger, A. L.; Rieger, P. H.; Richards, T. C.; GeigerId, W. E. Organometallics 1993, 12, 116;

(b) Goh, L.-Y.; D'aniello, M. J.; Slater, S.; Muetterties, E. L.; Tavanaiepour, I.; Chang, M. I.; Fredrich, M. F.; Day, V. W. Inorg. Chem. 1979, 18, 192.

[13] (a) Stender, M.; Oesen, H.; Blaurock, S.; Hey-Hawkins, E. Z. Anorg. Allg. Chem. 2001, 627, 980;

(b) Shin, J. H.; Savage, W.; Murphy, V. J.; Bonanno, J. B.; Churchill, D. G.; Parkin, G. J. Chem. Soc., Dalton Trans. 2001, 1732.

[14] Crystal structures: (a) Schultz, A. J.; Stearley, K. L.; Williams, J. M.; Mink, R.; Stucky, G. D. Inorg. Chem. 1977, 16, 3303;

(b) Koloski, T. S.; Pestana, D. C.; Carroll, P. J.; Berry, D. H. Organometallics 1994, 13, 489;

(c) Shin, J. H.; Churchill, D. G.; Bridgewater, B. M.; Pang, K.; Parkin, G. Inorg. Chim. Acta 2006, 359, 2942.

[15] (a) Hylakryspin, I.; Waldman, T. E.; Melendez, E.; Trakarnpruk, W.; Arif, A. M.; Ziegler, M. L.; Ernst, R. D.; Gleiter, R. Organometallics 1995, 14, 5030;

(b) Vos, D.; Arif, A. M.; Ernst, R. D. J. Organomet. Chem. 1998, 553, 277.

[16] (a) Kaupp, M.; Metz, B.; Stoll, H. Angew. Chem.-Int. Ed. 2000, 39, 4607;

(b) Kaupp, M.; Riedel, S. Inorg. Chim. Acta 2004, 357, 1865.

[17] GonzalezBlanco, O.; Branchadell, V. Organometallics 1997, 16, 5556.

[18] Bowmaker, G. A.; Schmidbaur, H.; Kruger, S.; Rosch, N. Inorg. Chem. 1997, 36, 1754.

[19] Gisdakis, P.; Antonczak, S.; Rosch, N. Organometallics 1999, 18, 5044.

[20] Tandura, S. N.; Shumsky, A. N.; Ugrak, B. I.; Negrebetsky, V. V.; Bylikin, S. Y.; Kolesnikov, S. P. Organometallics 2005, 24, 5227.

[21] (a) Feng, Y.; Liu, L.; Wang, J.-T.; Li, X.-S.; Guo, Q.-X. Chem. Commun. 2004, 88;

(b) Fang, Y.; Fan, J.-M.; Liu, L.; Li, X.-S.; Guo, Q.-X. Chem. Lett. 2002, 116;

(c) Li, X.-S.; Liu, L.; Schlegel, H. B. J. Am. Chem. Soc. 2002, 124, 9639.

铬族金属氢化物中M-H 键键能的从头计算

Ab Initio Calculation of M-H Bond Dissociation Energies of Cr-Group Metal Hydrides

PDF

补充材料

可视化

被引次数

摘要/Abstract

引用此文

分享此文

参考文献

相关文章 15

编辑推荐

相关统计

本文评价

[1]	熊昆, 陈伽瑶, 杨娜, 蒋尚坤, 李莉, 魏子栋. 理论探究水溶液条件对TMN_xC_y催化氮还原性能的增强机制[J]. 化学学报, 2021, 79(9): 1138-1145.
[2]	洪琪, 秦淼, 朱华. 复合物Kr-CS₂的一个新的四维的势能面及其红外光谱的预测[J]. 化学学报, 2018, 76(2): 138-142.
[3]	张千慧, 王阳, 刘翠, 杨忠志. 7,8-二氢-8-氧鸟嘌呤碱基对的量子化学研究[J]. 化学学报, 2014, 72(8): 956-962.
[4]	王丹丹, 巩春明, 朱权, 王健礼, 李象远. 乙苯与二甲苯在超临界压力下的热裂解研究[J]. 化学学报, 2013, 71(01): 88-92.
[5]	郭元茹潘清江. 异核d10-d8配合物结构与典型Au-Pt配合物激发态性质的理论研究[J]. 化学学报, 2009, 0(1): 27-32.
[6]	曾薇,丁涪江,赵可清. Au的乙炔配合物非线性光学性质的量子化学计算[J]. 化学学报, 2008, 66(17): 1935-1942.
[7]	余盛萍颜红袁秀香王欣 ʈ,田安民. Br^＋活化甲烷C—H键反应机理的理论研究[J]. 化学学报, 2008, 66(13): 1518-1522.
[8]	潘清江, 郭元茹, 张红星, 付宏刚. 双核Au(I)磷硫配合物激发态性质和金属间弱相互作用的从头算研究[J]. 化学学报, 2007, 65(7): 595-600.
[9]	林玲, 丁万见, 方维海, 于建国, 刘若庄. 硫代樟脑光化学反应的理论研究[J]. 化学学报, 2007, 65(3): 191-196.
[10]	闾春林, 刘永东, 王云海, 钟儒刚. 二甲胺与亚硝酸反应生成N,N-二甲基亚硝胺的理论研究[J]. 化学学报, 2007, 65(16): 1568-1572.
[11]	何云清,丁涪江,赵可清. 端基取代的长链硅烷二阶超极化率的量子化学研究[J]. 化学学报, 2006, 64(8): 799-805.
[12]	王金月,付小红,吴同,王健,肖慎修,胡常伟. 吲哚与亚烷基丙二酸二甲脂Michael加成反应机理的从头算研究[J]. 化学学报, 2006, 64(8): 727-732.
[13]	王郁文,钟凡,许亚萍,王学文. 牛磺酸与噻吩甲醛缩合形成Schiff碱反应机理的研究[J]. 化学学报, 2006, 64(8): 811-816.
[14]	田鹏, 宋溪明, 李莹, 段纪东, 梁志德, 张辉. 室温离子液体FeCl₃-BPC体系的研究[J]. 化学学报, 2006, 64(23): 2305-2309.
[15]	吴勇,薛英,谢代前. 邻氯甲苯光解反应机理的理论研究[J]. 化学学报, 2006, 64(2): 99-103.