It is reported in this paper that a tetraazamacrocyclic nickel complex NiL(CIO4,)2, where L is 2, 4, 4, 9, 11, 11-hexamethyl-1, 5, 8, 12 -tetraazacyclotetradeca- 1, 5, 8, 12- tetraene, can serve as oscillating catalys...It is reported in this paper that a tetraazamacrocyclic nickel complex NiL(CIO4,)2, where L is 2, 4, 4, 9, 11, 11-hexamethyl-1, 5, 8, 12 -tetraazacyclotetradeca- 1, 5, 8, 12- tetraene, can serve as oscillating catalyst in the system of NaBrO3-Pyr-H2SO4. The ranges of initial concentration of main reactants in the system were obtained. The influence of temperature, Vc, Br-, Ag+, Hg2+, acetonitrile or acrylamide on the oscillations were discussed. The results indicated that Br- played an important role controlling reaction progress and some free radicals.Br2 may be involved in the reaction process. The stirring rate can affect oscillating reactions. The oscillation trajectories of this system were recorded. They are different from classical BZ reactions and some other tetraazamacrocyclic complexes catalyzed systems. The mechanism is briefly discussed.展开更多
采用量子化学密度泛函B3LYP方法在6-31G**水平上研究了氮杂炔正离子[R C N CH(R1R2)]+与二环[2,2,1]2庚烯的反应机理.优化得到各驻点的几何构型,通过振动分析和内禀反应坐标对过渡态进行了确认,解析了反应路径;并在同一水平上研究了当R...采用量子化学密度泛函B3LYP方法在6-31G**水平上研究了氮杂炔正离子[R C N CH(R1R2)]+与二环[2,2,1]2庚烯的反应机理.优化得到各驻点的几何构型,通过振动分析和内禀反应坐标对过渡态进行了确认,解析了反应路径;并在同一水平上研究了当R,R1和R2分别为不同烷烃取代基的同分异构体时,得到不同产物的反应情况,找出这类反应随取代基不同的变化规律.展开更多
文摘It is reported in this paper that a tetraazamacrocyclic nickel complex NiL(CIO4,)2, where L is 2, 4, 4, 9, 11, 11-hexamethyl-1, 5, 8, 12 -tetraazacyclotetradeca- 1, 5, 8, 12- tetraene, can serve as oscillating catalyst in the system of NaBrO3-Pyr-H2SO4. The ranges of initial concentration of main reactants in the system were obtained. The influence of temperature, Vc, Br-, Ag+, Hg2+, acetonitrile or acrylamide on the oscillations were discussed. The results indicated that Br- played an important role controlling reaction progress and some free radicals.Br2 may be involved in the reaction process. The stirring rate can affect oscillating reactions. The oscillation trajectories of this system were recorded. They are different from classical BZ reactions and some other tetraazamacrocyclic complexes catalyzed systems. The mechanism is briefly discussed.
文摘采用量子化学密度泛函B3LYP方法在6-31G**水平上研究了氮杂炔正离子[R C N CH(R1R2)]+与二环[2,2,1]2庚烯的反应机理.优化得到各驻点的几何构型,通过振动分析和内禀反应坐标对过渡态进行了确认,解析了反应路径;并在同一水平上研究了当R,R1和R2分别为不同烷烃取代基的同分异构体时,得到不同产物的反应情况,找出这类反应随取代基不同的变化规律.
