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
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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)