金属大环配合物与咪唑类化合物轴向配位快速反应动力学研究

The Kinetic Study on the Axial Coordination Faster Reaction ofthe Metal Acrocyclic Complexes on Imidazole Compounds

模拟维生素Ｂ１２，合成了水溶性的高氯酸二氯合５，７，７，１２，１４，１４六甲基１，４，８，１１四氮杂环十四４，１１二烯钴（Ⅲ）配合物，用先进的ＵｎｉｏｎＧｉｋｅｎＲＡ４０１停流分光光度计首次对甲硝唑等四种咪唑类化合物与该配合物的轴向配位快速反应动力学性质进行了研究，探讨了它们的反应机理，对实验数据进行了拟合处理，得到预平衡步的平衡常数Ｋ和速控步的速率常数ｋ，并算出了预平衡步的ΔｒＨ０—ｍ，ΔｒＳ０—ｍ以及速控步的活化参数ΔｒＨ≠ｍ，ΔｒＳ≠ｍ．

The dichloro(5,7,7,12,14,14hexamethyl1,4,8,11tetraazacyclotetradeca4,11,diene)cobalt()perchlorate32N4)Cl2]ClO4 was prepared by imitating vitamin B12.The kinetic study on axial coordination faster reaction of 2]ClO4 of four imidazolates compounds at different temperatures by means of the union Giken RA401 stoppedflow was reported.The mechanism of the reaction was postulated.The equilibrium constants K of the preequilibrium step and the rate constants k of ratedeterming step were evaluated.The rH0 m,rS0 m of a preequilibrium step and rHm,rSm of a ratedetermining step were also calculated.