Theoretical Studies on the Cu-Cu Interaction and Stability of [Cua(Ph2Ppy)b(CH3CN)c]a (a = 1～2, b = 1～3, c = 0～2)

作者：XIE Mei Xiang; XU Xuan; HUANG Xiao Xuan

来源：结构化学, 2010, 29(5): 668-675.

• DFT (PBE0)
• NBO
• Cu-Cu interactions
• stabilities

To study the Cu-Cu interaction and stability of the title complexes, the structures of complexes [Cu(Ph2Ppy)(CH3CN)] 1, [Cu(Ph2Ppy)] 2, [Cu2(Ph2Ppy)2(CH3CN)2]2 3,[Cu2(Ph2Ppy)2(CH3CN)]2 4, [Cu2(Ph2Ppy)2]2 5 and [Cu2(Ph2Ppy)3(CH3CN)]2 6 were calculated by density functional theory PBE0 method, and the following conclusions can be drawn: (1) There is no orbital overlapping between two Cu atoms, indicating no Cu-Cu orbital interaction exists in complexes 3～6. Due to a breakdown of the closed shell configuration of Cu atoms, the weak Cu-Cu interactions result from the 3dCu → 4sCu' charge-transfer in 4～6. The Cu-Cu interaction strength follows 5 ＞ 6 ＞ 4, implying that there are stronger Cu-Cu interactions in the complexes with fewer CH3CN or more Ph2Ppy ligands. (2) The calculated interaction energies suggest that the coordination of Cu to Ph2Ppy is stronger than that to CH3CN. In 3～6, there are weaker interactions between Cu and CH3CN or Ph2Ppy in the complexes with more CH3CN or Ph2Ppy ligands. (3) The P-Cu and N-Cu interactions are much stronger than the Cu-Cu interaction, so we mainly attribute the stabilities of the binuclear complexes to the eight-membered rings Cu2P2N2C2.

• 单位
  华南师范大学