二苯并四氮杂[14]轮烯金属配合物电子结构和性质

用量子化学半经验方法和从头算对二苯并四氮杂[14]轮烯（Tmtaa)离子及其金属配合物的电子结构进行了详细的研究.讨论了轮烯金属配合物合成的模板效应及金属离子半径大小对模板效应的影响作用,对其亲电取代反应的活性位置作了相应理论解释.依据理论计算结果指导了轮烯配合物的定向亲电取代反应及新金属配合物的合成尝试,理论计算与实验事实基本一致.Tmtaa-Ni等配合物及其亲电取代反应产物的1HNMR谱、19FNMR谱表明金属配合物中金属离子对位C7、C16上的H原子被取代,与理论计算结果十分一致.

The Electronic Structure and Properties of 5,14-Dihydro-6,8,15,17-tetramethydibenzo [b,I][1,4,8,11] tetraaza [14]annulene and Its Metal Complexes

The electronic structure,metal template effect and electrophilic substitution of 5,14-Dihydro-6,8,15,17-tetramethydibenzo [b,i][1,4,8,11] tetraaza [14] annulene and its metal complexes have been studied by using semi-empiracal method of quantum chemistry program package MOAN and ab initio of Gaussian 94.All the geometry of the metal complexes have been optimized at the level of B3LYP/6-31＋G(d).The calculated results indicated that the magnitude of metal ion radii effected the metal template to synthesize the metal complexes,in accordance to the experimental yield of the products.The active site and reactivity of electrophilic substitution was described at C7、C16.Theoretical calculation leaded to the achievement of orientation reaction of the metal complexes and the synthesis of some metal complexes .The hydrogen atoms at C7、C16 of metal complex were replaced,which were proved by 1HNMR and 19FNMR.