Citation: MA Hua-Xuan, ZHENG Yan-Ling, ZHAN Yi-Shi, TAN Ying, HUANG Xiao, PENG Qi, XU Xuan. The Cr—Cr Bonding Character in Metal String Complexes [Cr₃(dpa)₄LL'] (dpa=dipyridylamide; L, L'=Cl, BF₄, CCPh)[J]. Acta Physico-Chimica Sinica, ;2012, 28(07): 1637-1644. doi: 10.3866/PKU.WHXB201204111 shu

The Cr—Cr Bonding Character in Metal String Complexes [Cr₃(dpa)₄LL'] (dpa=dipyridylamide; L, L'=Cl, BF₄, CCPh)

MA Hua-Xuan ¹ ,
ZHENG Yan-Ling ¹ ,
ZHAN Yi-Shi ¹ ,
TAN Ying ¹ ,
HUANG Xiao ¹ ,
PENG Qi ¹ ,
XU Xuan ^1,2,3,4,

1.
1. School of Chemistry & Environment, South China Normal University, Guangzhou 510006, P. R. China;
2. Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, Guangzhou 510006, P. R. China;
3. Key Laboratory of Electrochemical Technology on Energy Storage and Power Generation in Guangdong Universities, Guangzhou 510006, P. R. China;
4. Engineering Research Center of Materials and Technology for Electrochemical Energy Storage, Ministry of Education, South China Normal University, Guangzhou 510006, P. R. China

Received Date: 23 February 2012
Available Online: 11 April 2012
Fund Project: 广东省自然科学资金项目(9151063101000037) (9151063101000037) 广东省教育部产学研项目(2010B090400184) (2010B090400184) 广东省人才引进专项资金(C10133) (C10133)广州市科技攻关项目(2011J4300063)资助 (2011J4300063)

To study the configuration, the metal-metal interactions and the influences of axial ligands L and L' on the Cr—Cr bond in metal string complexes Cr₃(dpa)₄LL' (L, L'=Cl, BF₄, CCPh), the structures of complexes Cr₃(dpa)₄Cl₂ (1), Cr₃(dpa)₄(BF₄)2 (2), Cr₃(dpa)₄Cl(BF₄) (3), Cr₃(dpa)₄(CCPh)2 (4) and Cr₃(dpa)₄Cl(CCPh) (5) were investigated by density functional theory UBP86 method. The conclusions can be drawn as follows: (1) The complex with longer average Cr—Cr distance tends to form a symmetrical configuration, while it tends to form a asymmetric configuration with shorter average Cr—Cr distance. The most stable spin states, quintet states, with the longest average Cr—Cr distance tend to form a symmetrical configuration, while septuplet states with shortest Cr—Cr distance tend to form asymmetrical one; (2) For quintet states of all complexes, there is only a 3-center-3-electron σ bond in Cr₃⁶⁺ chain. Furthermore, except the σ bond, there are weak π Cr—Cr interactions in complex 2 and 3. For septuplet states, there is a triple bond in the short Cr—Cr bond of complexes 1-3 and 5, while there is only a 3-center-3-electron σ bond in complex 4. Not only in symmetrical configuration but also in asymmetric configuration, there are σ delocalizations in Cr₃⁶⁺ chain, suggesting the asymmetrical metal string complexes are still the potential molecular wire species; (3) The interactions between axial ligand L and Cr atom mainly correspond to the n_L→4_{s_Cr} and n_L→3_dz²Cr delocalizations. In addition, for stronger σ donor CCPh^- ligand, there are σ_C—C→4_{s_Cr} delocalizations as well. The order of the bond strength of axial ligand L and Cr atom is 2＜3＜1＜5＜4. The strongest bonding between CCPh^- ligand and Cr atom weakens the Cr—Cr bond and lengthens the Cr—Cr distance. Therefore, every spin state of 4 tends to form a symmetrical configuration.
- Metal string complexes,
- Density functional theory,
- Natural bond orbital,
- Metal-metal interaction
1. [1]
  
  (1) Wu, L. P.; Field, P.; Morrissey, T.; Murphy, C.; Nagle, P.;Hathaway, B.; Simmons, C.; Thornton, P. J. Chem. Soc. Dalton Trans. 1990, 12, 3835.
2. [2]
  (2) Aduldecha, S.; Hathaway, B. J. Chem. Soc. Dalton. Trans. 1991,4, 993.
3. [3]
  (3) Cotton, F. A.; Feng, X. J. J. Am. Chem. Soc. 1997, 119, 7514.doi: 10.1021/ja9705351
4. [4]
  (4) Cotton, F. A.; Daniels, L. M.; Murillo, C. A.; Pascual, I. J. Am. Chem. Soc. 1997, 119, 10223. doi: 10.1021/ja971998+
5. [5]
  (5) Clérac, R.; Cotton, F. A.; Daniels, L. M.; Dunbar, K. R.;Murillo, C. A.; Pascual, I. Inorg. Chem. 2000, 39, 748.doi: 10.1021/ic990793u
6. [6]
  (6) Clérac, R.; Cotton, F. A.; Daniels, L. M.; Dunbar, K. R.;Murillo, C. A.; Zhou, H. C. Inorg. Chem. 2000, 39, 3414.doi: 10.1021/ic0001964
7. [7]
  (7) Clérac, R.; Cotton, F. A.; Dunbar, K. R.; Lu, T.; Murillo, C. A.;Wang, X. J. Am. Chem. Soc. 2000, 122, 2272. doi: 10.1021/ja994051b
8. [8]
  (8) Cotton, F. A.; Daniels, L. M.; Lei, P.; Murillo, C. A.;Wang, X.Inorg. Chem. 2001, 40, 2778. doi: 10.1021/ic001376g
9. [9]
  (9) Berry, J. F.; Cotton, F. A.; Lu, T. J. Am. Chem. Soc. 2004, 126,7082. doi: 10.1021/ja049055h
10. [10]
  (10) Sheu, J. T.; Lin, C. C.; Chao, I.;Wang, C. C.; Peng, S. M. Chem. Commun. 1996, 315.
11. [11]
  (11) Shieh, S. J.; Chou, C. C.; Lee, G. H.;Wang, C. C.; Peng, S. M.Angew. Chem. Int. Edit. 1997, 36, 56. doi: 10.1002/anie.199700561
12. [12]
  (12) Lai, S. Y.; Lin, T.W.; Chen, Y. H.;Wang, C. C.; Lee, G. H.;Yang, M.; Leung, M.; Peng, S. M. J. Am. Chem. Soc. 1999, 121,250. doi: 10.1021/ja982065w
13. [13]
  (13) Peng, S. M.;Wang, C. C.; Jang, Y. L.; Chen, Y. H.; Li, F. Y.;Mou, C. Y.; Leung, M. K. J. Mag. Mag. Mater. 2000, 209, 80.doi: 10.1016/S0304-8853(99)00650-2
14. [14]
  (14) Zhu, L. G.; Peng, X. M. Chinese Journal of Inorganic Chemistry 2002, 18, 117. [朱龙观, 彭旭明. 无机化学学报,2002, 18, 117.] doi: 10.3321/j.issn:1001-4861.2002.02.001
15. [15]
  (15) Chen, I.W. P.; Fu, M. D.; Tseng,W. H.; Yu, J. Y.;Wu, S. H.; Ku,C. J.; Chen, C. H.; Peng, S. M. Angew. Chem. Int. Edit. 2006,118, 5946. doi: 10.1002/ange.200600800
16. [16]
  (16) Hsiao, C. J.; Lai, S. H.; Chen, I. C.;Wang,W. Z.; Peng, S. M.J. Phys. Chem. A 2008, 112, 13528. doi: 10.1021/jp8081326
17. [17]
  (17) Ismayilov, R. H.;Wang,W. Z.; Lee, G. H.; Yeh, C. Y.; Hua, S.A.; Song, Y.; Rohmer, M. M.; Bénard, M.; Peng, S. M. Angew. Chem. Int. Edit. 2011, 50, 2045. doi: 10.1002/anie.201006695
18. [18]
  (18) Benbellat, N.; Rohmer, M. M.; Bénard, M. Chem. Commun.2001, 2368.
19. [19]
  (19) Rohmer, M. M.; Bénard, M. J. Clust. Sci. 2002, 13, 333. doi: 10.1023/A:1020546915168
20. [20]
  (20) Wu, D. Y.; Zhang, T. L. Progress in Chemistry 2004, 16, 911.[吴德有, 张天乐. 化学进展, 2004, 16, 911.]
21. [21]
  (21) Becke, A. D. Phys. Rev. A 1988, 38, 3098. doi: 10.1103/PhysRevA.38.3098
22. [22]
  (22) Perdew, J. P. Phys. Rev. B 1986, 33, 8822. doi: 10.1103/PhysRevB.33.8822
23. [23]
  (23) Hay, P. J.;Wadt,W. R. J. Chem. Phys. 1985, 82, 299. doi: 10.1063/1.448975
24. [24]
  (24) Glendening, E. D.; Reed, A. E.; Carpenter J. E. NBO Version 3.1.
25. [25]
  (25) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B. et al. Gaussian 03,Revision C.02; Gaussian Inc:Wallingford, CT, 2003.
26. [26]
  (26) Carpenter, J. E.;Weinhold, F. J. Mol. Struct. -Theochem 1988,169, 41. doi: 10.1016/0166-1280(88)80248-3
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The Cr—Cr Bonding Character in Metal String Complexes [Cr3(dpa)4LL'] (dpa=dipyridylamide; L, L'=Cl, BF4, CCPh)

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通讯作者: 陈斌, bchen63@163.com

The Cr—Cr Bonding Character in Metal String Complexes [Cr₃(dpa)₄LL'] (dpa=dipyridylamide; L, L'=Cl, BF₄, CCPh)