三聚氰胺对金属(Ⅱ)卟啉反应活性影响的概念密度泛函研究

选取8个典型的二价金属卟啉MP(M=Ca,Mg,Zn,Cu,Ni,Fe,Co,Mn)与三聚氰胺(L)形成轴向金属配合物(L-MP),应用概念密度泛函工具,系统地计算和比较了L键合前后对其结构和反应性质的影响.结果表明:除钙的特别不稳定物外,L配体对其余6种MP的结构影响较小,它们有较高的化学势指数和较低的总化学硬度而趋向配体的解离;与铁卟啉能形成最稳定的轴向配合物,电子由配体N原子流向铁,中心铁的亲核Fukui指数值大于体系里其他原子的Fukui指数,且发生符号改变.在这些典型的赤道键合配合物中,金属M、配体N之间的二级微扰相互作用能,自然电荷布局以及概念密度泛函指数等方面,存在着一系列线性关系.以上结果可为体内三聚氰胺致结石提供新的启示.

Investigation on the reactivity properties of melamine coordinated molecules on the activity of heme in conceptual DFT method

By the employment of density functional theory(DFT),conceptual DFT approaches,structure and reactivity properties of melamine(L)and its metal porphin complexes(L-MP,M=Ca,Mg,Fe,Co,Cu,Mn,Zn,Ni)are systematically studied for a selection of divalent metal cations.We found that L-MP complexes are structurally different from their precursors and more reactive in electrophilic and nucleophilic reactions for L-FeP complexes.A few quantitative linear relationships have been discovered between bonding interactions,ch...