β二酮二亚胺Zn配合物的理论研究
摘要
对过渡金属与β二酮二亚胺配体形成的配位化合物的研究是金属有机化学里的一个重要研究领域。同时,因为β二酮二亚胺配体对过渡金属的立体和电子效应,相关研究已经诞生了许多高效催化剂.
本论文在B3LYP水平上,选用适当的基组对一系列的β二酮二亚胺配合物进行了结构优化,在相同的水平下,对优化得到的配合物的稳定结构进行自然键轨道(NBO)分析。在平衡构型的基础上,对各临界点进行电荷密度的拓扑分析。并计算了相关化合物的解离能。
对于RM(μ-X)_2Li(OEt_2)_2(R=[{(C_6H_3)N(Me)C}_2CH])的含有不同过渡金属(X=I;M=Cu,Zn,Cd)及不同卤素(X=Br,Cl,F;M=Zn)化合物,研究表明对于含有不同卤素,相同过渡金属Zn的配位化合物,随着卤素半径减小,Zn-Li和Zn-X距离减小,Zn-X键级和稳定化能减小。而Zn,X带电荷数上升,结合能上升,稳定性逐渐增大。对于含有相同卤素I,不同过渡金属的配合物,同族的Zn,Cd的化合物之间区别不大。但与Zn同周期缺少价电子的Cu的化合物结合能很小。过渡金属M所带电荷大小顺序为Cu 对于LZn(μ-X)_2ZnL(L={HC(CMeNPh)_2})的不同桥接基团(X=F,OH,NH_2,Cl,SH,PH_2)的配位化合物,研究表明配位化合物四元桥环按F 本文同时还对RZn-ZnR(R=[{-PhN(Me)C}_2CH])配位化合物和含有负氢桥原子的HC(CMeNAr)_2Zn(μ-H)_2BH_2配位化合物进行了自然键轨道(NBO)和AIM分析。分析表明以上两者都具有较为稳定的结构。
The compounds formed with transition metal andβ-diketiminate ligands are important in research of organometallic chemistry.β-diketiminate ligands can regulate metal center on stereo and electronic effects. Therefore, the studies of the compound have obtained much efficient catalysts.
In this paper, a series ofβ-diketiminate complex structures have been optimized in the B3LYP level and an appropriate basis set selected. In the same level, natural bond orbital (NBO) analysis has been applied in the optimized structure of compounds. On the equilibrium geometries, the charge density topological analysis of critical points has been achieved. In addition, the dissociation-energy of related compounds has been calculated.
For RM(μ-X)_2Li(OEt_2)_2(R=[{(C_6H_3)N(Me)C}_2CH]) compounds containing different transition metals (X = I; M = Cu, Zn, Cd) and different halogen (X = Br, Cl, F; M = Zn), the study shows that Zn-Xbond order and stabilization are reduced with decrease of the halogen radius, Zn-Li and Zn-X distance, in the condition of containing different halogens, same transition metal Zn compound. Charge of Zn and X, binding energy and stability increase gradually. In the condition of containing same halogen I, different transition metal, it is not obvious difference between Zn and Cd. However, Cu compound which lacks valence electron has small binding energy. The order of charge at M is Cu For compounds LZn(μ-X)_2ZnL(L={HC(CMeNPh)_2}) containing different bridged groups (X=F, OH, NH_2, Cl, SH, PH_2), the study shows that the stability of bridged four-membered ring gradually increases in ascending order, i.e., F This paper also has optimized RZn-ZnR(R=[{-PhN(Me)C}_2CH]) coordination compound and HC(CMeNAr)_2Zn(μ-H)_2BH_2 coordination compound. Then, these compounds are analyzed in terms of Natural Bond orbital analysis(NBO) and atom in molecular analysis(AIM). The above analysis indicates that both of these compounds stay in stable structures.
本论文在B3LYP水平上,选用适当的基组对一系列的β二酮二亚胺配合物进行了结构优化,在相同的水平下,对优化得到的配合物的稳定结构进行自然键轨道(NBO)分析。在平衡构型的基础上,对各临界点进行电荷密度的拓扑分析。并计算了相关化合物的解离能。
对于RM(μ-X)_2Li(OEt_2)_2(R=[{(C_6H_3)N(Me)C}_2CH])的含有不同过渡金属(X=I;M=Cu,Zn,Cd)及不同卤素(X=Br,Cl,F;M=Zn)化合物,研究表明对于含有不同卤素,相同过渡金属Zn的配位化合物,随着卤素半径减小,Zn-Li和Zn-X距离减小,Zn-X键级和稳定化能减小。而Zn,X带电荷数上升,结合能上升,稳定性逐渐增大。对于含有相同卤素I,不同过渡金属的配合物,同族的Zn,Cd的化合物之间区别不大。但与Zn同周期缺少价电子的Cu的化合物结合能很小。过渡金属M所带电荷大小顺序为Cu
The compounds formed with transition metal andβ-diketiminate ligands are important in research of organometallic chemistry.β-diketiminate ligands can regulate metal center on stereo and electronic effects. Therefore, the studies of the compound have obtained much efficient catalysts.
In this paper, a series ofβ-diketiminate complex structures have been optimized in the B3LYP level and an appropriate basis set selected. In the same level, natural bond orbital (NBO) analysis has been applied in the optimized structure of compounds. On the equilibrium geometries, the charge density topological analysis of critical points has been achieved. In addition, the dissociation-energy of related compounds has been calculated.
For RM(μ-X)_2Li(OEt_2)_2(R=[{(C_6H_3)N(Me)C}_2CH]) compounds containing different transition metals (X = I; M = Cu, Zn, Cd) and different halogen (X = Br, Cl, F; M = Zn), the study shows that Zn-Xbond order and stabilization are reduced with decrease of the halogen radius, Zn-Li and Zn-X distance, in the condition of containing different halogens, same transition metal Zn compound. Charge of Zn and X, binding energy and stability increase gradually. In the condition of containing same halogen I, different transition metal, it is not obvious difference between Zn and Cd. However, Cu compound which lacks valence electron has small binding energy. The order of charge at M is Cu
引文
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