取代基对咔咯锰(V)-氧配合物Mn―O的成键影响

引用本文: 何婧, 徐志广, 曾允秀, 许旋, 喻兰, 王琦, 刘海洋. 取代基对咔咯锰(V)-氧配合物Mn―O的成键影响[J]. 物理化学学报, 2012, 28(07): 1658-1664. doi: 10.3866/PKU.WHXB201205101 shu

Citation: HE Jing, XU Zhi-Guang, ZENG Yun-Xiu, XU Xuan, YU Lan, WANG Qi, LIU Hai-Yang. Effect of Substituents on Mn―O Bond in Oxo-Manganese(V) Corrole Complexes[J]. Acta Physico-Chimica Sinica, 2012, 28(07): 1658-1664. doi: 10.3866/PKU.WHXB201205101 shu

取代基对咔咯锰(V)-氧配合物Mn―O的成键影响

何婧 ^1, ,
徐志广 ^1, ,
曾允秀 ^1, ,
许旋 ^1, ,
喻兰 ^2, ,
王琦 ^2, ,
刘海洋 ^2,

基金项目:
国家自然科学基金(20971046, 21171057) (20971046, 21171057)

广东省自然科学基金(10351064101000000)资助项目 (10351064101000000)

摘要:

用密度泛函理论(DFT)方法对一系列A₃型咔咯锰(V)氧配合物进行了理论计算. 结果表明: 咔咯锰(V)-氧配合物中Mn―O键是由1 个σ键和2 个π键构成的叁键结构; 当咔咯中位取代基由推电子过渡到拉电子性质时, 咔咯骨架紧缩, Mn―O键缩短, 其拉曼光谱的伸缩振动峰往高波数移动; 取代基与氧原子的静电作用模式由正-负吸引转化为负-负排斥, 导致Mn―O键解离能ΔE减少, 即拉电子基团有利于增强咔咯锰(V)-氧配合物氧原子的活泼性.

关键词:

English

Effect of Substituents on Mn―O Bond in Oxo-Manganese(V) Corrole Complexes

1.
1. Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University; Guangzhou 510006, P. R. China;
2. Department of Chemistry, South China University of Technology, Guangzhou 510641, P. R. China
Received Date: 10 January 2012
Available Online: 07 June 2012
Fund Project:
国家自然科学基金(20971046, 21171057)

广东省自然科学基金(10351064101000000)资助项目

Abstract:

Density functional theory (DFT) calculations are used to investigate the effect of substituents on the Mn―O bond in A3-type oxo-manganese(V) corrole complexes. Results indicate that the Mn―O bonds in all the investigated oxo-manganese(V) corrole complexes are triply bonded by one σ and two π bonds. As the electron withdrawing ability of the substituents increases, the corrole skeleton contracts, resulting in a decrease in the Mn―O bond length, and the Mn―O Raman stretching vibration shifts to higher wavenumber. As the electrostatic potential of the substituents changes from positive to negative, the electrostatic interaction between oxygen and substituents changes from a negative-positive electrostatic attraction to a negative-negative electrostatic repulsion. Electron withdrawing substituents enhance oxygen reactivity of corrole Mn-oxo complexes by lowering the Mn―O bond dissociation energy.

Key words:

1. [1]
  
  (1) Reedijk, J. Bioinorganic Catalysis; Reedijk, J. Ed.; MarcelDekker Inc.: New York, 1993; pp 347-393.
  (1) Reedijk, J. Bioinorganic Catalysis; Reedijk, J. Ed.; MarcelDekker Inc.: New York, 1993; pp 347-393.
2. [2]
  (2) Meunier, B. Biomimetic Oxidations Catalyzed by Transition Metal Complexes; Meunier, B. Ed.; Imperial College Press:London, 2000.(2) Meunier, B. Biomimetic Oxidations Catalyzed by Transition Metal Complexes; Meunier, B. Ed.; Imperial College Press:London, 2000.
3. [3]
  (3) Sheldon, R. A. Metalloporphyrins in Catalytic Oxidations;Sheldon, R. A. Ed.; Marcel Dekker Inc.: New York, 1994.(3) Sheldon, R. A. Metalloporphyrins in Catalytic Oxidations;Sheldon, R. A. Ed.; Marcel Dekker Inc.: New York, 1994.
4. [4]
  (4) Yagi, M.; Kaneko, M. Chem. Rev. 2001, 101, 21. doi: 10.1021/cr980108l(4) Yagi, M.; Kaneko, M. Chem. Rev. 2001, 101, 21. doi: 10.1021/cr980108l
5. [5]
  (5) Rebelo, S. L. H.; Pereira, M. M.; Simões, M. M. Q.; Neves, M.G.; Cavaleiro, J. A. S. J. Catal. 2005, 234, 76. doi: 10.1016/j.jcat.2005.05.026(5) Rebelo, S. L. H.; Pereira, M. M.; Simões, M. M. Q.; Neves, M.G.; Cavaleiro, J. A. S. J. Catal. 2005, 234, 76. doi: 10.1016/j.jcat.2005.05.026
6. [6]
  (6) Gross, Z.; Galili, N.; Saltsman, I. Angew. Chem. Int. Edit. 1999,38, 1427. doi: 10.1002/(SICI)1521-3773(19990517)38:10<1427::AID-ANIE1427>3.0.CO;2-1(6) Gross, Z.; Galili, N.; Saltsman, I. Angew. Chem. Int. Edit. 1999,38, 1427. doi: 10.1002/(SICI)1521-3773(19990517)38:10<1427::AID-ANIE1427>3.0.CO;2-1
7. [7]
  (7) Gryko, D. T.; Koszarna, B. Org. Biomol. Chem. 2003, 1, 350.doi: 10.1039/b208950e(7) Gryko, D. T.; Koszarna, B. Org. Biomol. Chem. 2003, 1, 350.doi: 10.1039/b208950e
8. [8]
  (8) lubkov, G.; Bendix, J.; Gray, H. B.; Mahammed, A.; ldberg, I.; DiBilio, A. J.; Gross, Z. Angew. Chem. Int. Edit.2001, 40, 2132. doi: 10.1002/1521-3773(20010601)40:11<2132::AID-ANIE2132>3.0.CO;2-5(8) lubkov, G.; Bendix, J.; Gray, H. B.; Mahammed, A.; ldberg, I.; DiBilio, A. J.; Gross, Z. Angew. Chem. Int. Edit.2001, 40, 2132. doi: 10.1002/1521-3773(20010601)40:11<2132::AID-ANIE2132>3.0.CO;2-5
9. [9]
  (9) Gross, Z.; lubkov, G.; Simkhovich, L. Angew. Chem. Int. Edit. 2000, 39, 4045. doi: 10.1002/1521-3773(20001117)39:22<4045::AID-ANIE4045>3.0.CO;2-P(9) Gross, Z.; lubkov, G.; Simkhovich, L. Angew. Chem. Int. Edit. 2000, 39, 4045. doi: 10.1002/1521-3773(20001117)39:22<4045::AID-ANIE4045>3.0.CO;2-P
10. [10]
  (10) de Visser, S. P.; Ogliaro, F.; Gross, Z.; Shaik, S. Chem. Eur. J.2001, 7, 4954. doi: 10.1002/1521-3765(20011119)7:22<4954::AID-CHEM4954>3.0.CO;2-U(10) de Visser, S. P.; Ogliaro, F.; Gross, Z.; Shaik, S. Chem. Eur. J.2001, 7, 4954. doi: 10.1002/1521-3765(20011119)7:22<4954::AID-CHEM4954>3.0.CO;2-U
11. [11]
  (11) Liu, H. Y.; Lai, T. S.; Yeung, L. L.; Chang, C. K. Org. Lett.2003, 5, 617. doi: 10.1021/ol027111i(11) Liu, H. Y.; Lai, T. S.; Yeung, L. L.; Chang, C. K. Org. Lett.2003, 5, 617. doi: 10.1021/ol027111i
12. [12]
  (12) Liu, H. Y.; Yam, F.; Xie, Y. T.; Li, X. Y.; Chang, C. K. J. Am. Chem. Soc. 2009, 131, 12890. doi: 10.1021/ja905153r(12) Liu, H. Y.; Yam, F.; Xie, Y. T.; Li, X. Y.; Chang, C. K. J. Am. Chem. Soc. 2009, 131, 12890. doi: 10.1021/ja905153r
13. [13]
  (13) Gao, Y.; Akermark, T.; Liu, J. H.; Sun, L. C.; Akermark, B.J. Am. Chem. Soc. 2009, 131, 8726. doi: 10.1021/ja901139r(13) Gao, Y.; Akermark, T.; Liu, J. H.; Sun, L. C.; Akermark, B.J. Am. Chem. Soc. 2009, 131, 8726. doi: 10.1021/ja901139r
14. [14]
  (14) Kim, S. H.; Park, H.; Seo, M. S.; Kubo, M.; Ogura, T.; Klajn, J.;Gryko, D. T.; Valentine, J. S.; Nam,W. J. Am. Chem. Soc. 2010,132, 14030. doi: 10.1021/ja1066465(14) Kim, S. H.; Park, H.; Seo, M. S.; Kubo, M.; Ogura, T.; Klajn, J.;Gryko, D. T.; Valentine, J. S.; Nam,W. J. Am. Chem. Soc. 2010,132, 14030. doi: 10.1021/ja1066465
15. [15]
  (15) Zhang, R.; Harishchandra, D. N.; Newcomb, M. Chem. Eur. J.2005, 11, 5713. doi: 10.1002/chem.200500134(15) Zhang, R.; Harishchandra, D. N.; Newcomb, M. Chem. Eur. J.2005, 11, 5713. doi: 10.1002/chem.200500134
16. [16]
  (16) Kumar, A.; ldberg, I.; Botoshansky, M.; Buchman, Y.; Gross,Z. J. Am. Chem. Soc. 2010, 132, 15233. doi: 10.1021/ja1050296(16) Kumar, A.; ldberg, I.; Botoshansky, M.; Buchman, Y.; Gross,Z. J. Am. Chem. Soc. 2010, 132, 15233. doi: 10.1021/ja1050296
17. [17]
  (17) Rong, C.; Lian, S.; Yin, D.; Zhong, A.; Zhang, R.; Liu, S. Chem. Phys. Lett. 2007, 434, 149. doi: 10.1016/j.cplett.2006.11.092(17) Rong, C.; Lian, S.; Yin, D.; Zhong, A.; Zhang, R.; Liu, S. Chem. Phys. Lett. 2007, 434, 149. doi: 10.1016/j.cplett.2006.11.092
18. [18]
  (18) Eikey, R. A.; Khan, S. I.; Abu-Omar, M. M. Angew. Chem. Int. Edit. 2002, 41, 3592.(18) Eikey, R. A.; Khan, S. I.; Abu-Omar, M. M. Angew. Chem. Int. Edit. 2002, 41, 3592.
19. [19]
  (19) Steene, E.;Wondimagegn, T.; Ghosh, A. J. Phys. Chem. B 2001,105, 11406. doi: 10.1021/jp012037r(19) Steene, E.;Wondimagegn, T.; Ghosh, A. J. Phys. Chem. B 2001,105, 11406. doi: 10.1021/jp012037r
20. [20]
  (20) Liu, H. Y.; Li, L.; Ying, X.;Wang, X. L.; Xu, Z. G.; Liao, S. J.;Chang, C. K. Acta Phys. -Chim. Sin. 2008, 24, 1602. [刘海洋, 李立, 应晓, 王湘利, 徐志广, 廖世军, 张启光. 物理化学学报, 2008, 24, 1602.] doi: 10.3866/PKU.WHXB20080913](20) Liu, H. Y.; Li, L.; Ying, X.;Wang, X. L.; Xu, Z. G.; Liao, S. J.;Chang, C. K. Acta Phys. -Chim. Sin. 2008, 24, 1602. [刘海洋, 李立, 应晓, 王湘利, 徐志广, 廖世军, 张启光. 物理化学学报, 2008, 24, 1602.] doi: 10.3866/PKU.WHXB20080913]
21. [21]
  (21) Reed, A. E.; Curtiss, L. A.;Weinhold, F. Chem. Rev. 1988, 88,899. doi: 10.1021/cr00088a005(21) Reed, A. E.; Curtiss, L. A.;Weinhold, F. Chem. Rev. 1988, 88,899. doi: 10.1021/cr00088a005
22. [22]
  (22) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03,Revision A.01; Gaussian Inc.: Pittsburgh, PA, 2003.(22) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03,Revision A.01; Gaussian Inc.: Pittsburgh, PA, 2003.
23. [23]
  (23) Miller, C. G.; rdon-Wylie, S.W.; Horwitz, C. P.; Strazisar, S.A.; Peraino, D. K.; Clark, G. R.;Weintraub, S. T.; Collins, T. J.J. Am. Chem. Soc. 1998, 120, 11540. doi: 10.1021/ja972922g(23) Miller, C. G.; rdon-Wylie, S.W.; Horwitz, C. P.; Strazisar, S.A.; Peraino, D. K.; Clark, G. R.;Weintraub, S. T.; Collins, T. J.J. Am. Chem. Soc. 1998, 120, 11540. doi: 10.1021/ja972922g
24. [24]
  (24) Mandimutsira, B. S.; Ramdhanie, B.; Todd, R. C.;Wang, H.;Zareba, A. A.; Czernuszewicz, R. S.; ldberg, D. P. J. Am. Chem. Soc. 2002, 124, 15170. doi: 10.1021/ja028651d(24) Mandimutsira, B. S.; Ramdhanie, B.; Todd, R. C.;Wang, H.;Zareba, A. A.; Czernuszewicz, R. S.; ldberg, D. P. J. Am. Chem. Soc. 2002, 124, 15170. doi: 10.1021/ja028651d
25. [25]
  (25) Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502. doi: 10.1021/jp960976r(25) Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502. doi: 10.1021/jp960976r
26. [26]
  (26) Ballhausen, C. J.; Gray, H. B. Inorg. Chem. 1962, 1, 111. doi: 10.1021/ic50001a022(26) Ballhausen, C. J.; Gray, H. B. Inorg. Chem. 1962, 1, 111. doi: 10.1021/ic50001a022
27. [27]
  (27) Workman, J. M.; Powell, R. D.; Procyk, A. D.; Collins, T. J.;Bocian, D. F. Inorg. Chem. 1992, 31, 1548. doi: 10.1021/ic00035a003(27) Workman, J. M.; Powell, R. D.; Procyk, A. D.; Collins, T. J.;Bocian, D. F. Inorg. Chem. 1992, 31, 1548. doi: 10.1021/ic00035a003
28. [28]
  (28) Jin, N.; Ibrahim. M.; Spiro, T. G.; Groves, J. T. J. Am. Chem. Soc. 2007, 129, 12416. doi: 10.1021/ja0761737(28) Jin, N.; Ibrahim. M.; Spiro, T. G.; Groves, J. T. J. Am. Chem. Soc. 2007, 129, 12416. doi: 10.1021/ja0761737
29. [29]
  (29) Shimazaki, Y.; Nagano, T.; Takesue, H.; Ye, B. H.; Tani, F.;Naruta, Y. Angew. Chem. Int. Edit. 2004, 43, 98. doi: 10.1002/anie.200352564(29) Shimazaki, Y.; Nagano, T.; Takesue, H.; Ye, B. H.; Tani, F.;Naruta, Y. Angew. Chem. Int. Edit. 2004, 43, 98. doi: 10.1002/anie.200352564
30. [30]
  (30) Liu, H. Y.; Zhou, H.; Liu, L. Y.; Ying, X.; Jiang, H. F.; Chang, C.K. Chem. Lett. 2007, 36, 274. doi: 10.1246/cl.2007.274
  (30) Liu, H. Y.; Zhou, H.; Liu, L. Y.; Ying, X.; Jiang, H. F.; Chang, C.K. Chem. Lett. 2007, 36, 274. doi: 10.1246/cl.2007.274

扫一扫看文章

计量

PDF下载量: 709
文章访问数: 2267
HTML全文浏览量: 15

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

取代基对咔咯锰(V)-氧配合物Mn―O的成键影响

English

Effect of Substituents on Mn―O Bond in Oxo-Manganese(V) Corrole Complexes

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

取代基对咔咯锰(V)-氧配合物Mn―O的成键影响

English

Effect of Substituents on Mn―O Bond in Oxo-Manganese(V) Corrole Complexes

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs