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
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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 nL→4sCr and nL→3dz2Cr delocalizations. In addition, for stronger σ donor CCPh- ligand, there are σC—C→4sCr 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.
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