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.
In order to study the Fe-Cu interactions and their effects on 31p NMR, the structures of mononuclear complex Fe（CO）3fPhzPpy）a 1 and binuclear complexes Fe（CO）3（PhEPpy）z（CuXn） （2： Xn = Cl2^2-, 3： Xn = Cl-, 4： Xn = Br-） are calculated by density functional theory （DFT） PBE0 method. For complexes 1, 3 and 4, the 31p NMR chemical shifts calculated by PBE0-GIAO method are in good agreement with experimental results. The 31p chemical shift is 82.10 ppm in the designed complex 2. The Fe-Cu interactions （including Fe→Cu and Fe←Cu charge transfer） mainly exhibit the indirect interactions. Moreover, the Fe-Cu（I） interactions （mostly acting as σFe-p→4Scu and aFe-C→4Scu charge transfer） in complexes 3 and 4 are stronger than Fe-Cu（Ⅱ） interactions （mostly acting as σFe-p→4Scu and σFe-p←4Sc,） in complex 2. In complex 2, the stronger Fe←Cu interac- tions, acting as σFe-p←44SCu charge transfer, increase the electron density on P nucleus, which causes the upfield 31p chemical shift compared with mononuclear complex 1. For 3 and 4, although a little deshielding for P nucleus is derived from the delocalization of σFe-p→4Scu due to the Fe→Cu interactions, the stronger σFe-c→np charge-transfer finally increases the electron density on P nucleus. As a result, an upfield 31p chemical shift is observed compared with 1. The stability follows the order of 2〉3=4, indicating that Fe（CO）3（PhzPpy）2（CuCl2） is stable and could be synthesized experimentally. The N-Cu（Ⅱ） interaction plays an important role in the stability of 2. Because the delocalization of σFe-p→4SCu and σFe-c→πc-o weakens the a bonds of Fe-C and ~r bonds of CO, it is favorable for increasing the catalytic activity of binuclear complexes. Complexes 3 and 4 are expected to show higher catalytic activity compared to 2.
To study the Fe-M interactions and their effects on 31p NMR, the structures of Fe（CO）3（EtPhPpy）2 1, Fe（CO）3（EtPhPpy）2M（NCS）2 （2： M=Zn, 3： M=Cd, 4： M=Hg） and Fe（CO）3（EtPhPpy）2CdX2 （5： X=C1, 6： X=SCN） were investigated by density functional theory （DFT） PBE0 method. The stabilities S of complexes follow S（2）〉S（3）〉S（4） and S（3）,.~S（6）〉S（5）, indicating that 6 is stable and may be synthesized. The complexes with thiocyanate are more stable than that with chloride in Fe（CO）3（EtPhPpy）2CdX2. The strength I of Fe-M interactions follows I（2）≈I（3）〈I（4）. The Fe-Cd interactions of 3 and 6, which contain thiocyanate, are stronger than that of 5 with chloride. The charge-transfer, which enhances with the increasing of Fe-M interaction strength, comes from Et, Ph, py, CO groups towards P, Fe, and M atoms. Because the delocalization of thiocyanate disperses the charge of M2＋, the charge-transfer of the complexes with thiocyanate is stronger than that with chloride. There is a a-bond between Fe and Hg atoms in 4. However, in binuclear complexes except 4, the Fe-M interactions act as nFe→nM, σP-Fe→nM and σC-Fe→nM delocalization, and the N-M interactions mainly act as nN→nM delocalization. In binuclear complexes, due to the Fe→M interactions, the strong σFe--C→σ＊Fe--p or σFe-Hg→σ＊Fe--I2 delocalization and the charge-transfer, the electron density on P nucleus is increased, and thus upfield 31p chemical shifts are caused （compared with mononuclear complex 1）.
