β二酮二亚胺Zn配合物桥联二聚体的理论研究

Theoretical study of dimeric β-diketiminate complexes of zinc with different bridging ligands

从理论上探讨和研究了LZn(μ-X)2ZnL(L={HC(CMeNPh)2})配位化合物的不同桥接基团衍生物的性质。采用B3LYP方法,选用6-31+G**基组对其进行了计算及分析。结果表明过渡金属与配体间存在广泛的电子给体-受体作用。在含有不同的桥接基团(X=F,OH,NH2,Cl,SH,PH2)的此类配位化合物间,当桥接基团分别为F,OH,NH2和Cl,SH,PH2时配位化合物四元桥环稳定性逐渐增强。同时从稳定性上讲,第2周期大于相应的第3周期桥联化合物。其中,带电荷数较低的PH2配位化合物有着较强的电子给体-受体作用,稳定化能较高。Wiberg键级也大于其他配位化合物,因而桥键比较稳定。

The properties of dimeric LZn （ μ-X ） 2ZnL （ L = { HC （CMeNAr） 2 / , Ar = 2,6-Me2 C6H3 ） complexes with different bridging groups have been analyzed using the B3LYP method with the 6-31 ＋ G^＊ ＊ basis set. The results show that there is a wide range of electronic donor-acceptor interactions between the transition metal Zn center and the ligands, The stability of the central four-membered ring varies with bridging ligand and increases gradually in the order F 〈 OH 〈 NH2 and Cl 〈 SH 〈 PH2. The stabilities of the compounds with first row elements as bridging ligands are greater than those of the corresponding compounds with second row elements. The PH2 coordination compound has a strong electronic donor-acceptor interaction with low charge separation and the PH2 coordination compound has a relatively high stabilization energy. It also has a higher Wiberg bond order than the other compounds, confirming the relatively high stability of the bridge bond in this compound.