11,12,13-三甲基-1,4,7,10-四氮杂十三环-10,13-二烯-镍(II)配合物催化的新型振荡化学反应

本文报道了一种新型振荡化学反应体系--BrOˉ~3-MA-H2SO4-Ni(L-H)]X(X为配阴离子)体系, 其中MA为丙二酸, L代表题给大环11,12,13-三甲基-1,4,7,10-四氮杂十三 环-10, 13-二烯。测得了该体系发生振荡的组分浓度范围; 研究了各物浓度、自由基抑制剂和还原剂对振荡反应的影响; 还测得了振荡的轨迹为螺旋线而非极限环, 由于催化剂消耗振荡衰减; 初步提出了振荡反应发生的可能机理。

New oscillating reactions catalyzed by a macrocyclic nickel (II)complex with the ligand 11,12,13-trimethyl-1,4,7,10-tetraazacycotrideca-10,13-diene

New oscillating reactions with the participation of the title macrocyclic Ni(II) complex ion NiL]2+ as catalyst in acidic bromate medium were studied. The concentration oscillations of this system are damped rapidly due to the consumption of the catalyst. Malonic acid or acetone can serve as organic substrate to produce oscillations. Glycocoll cannot serve as the organic substrate to give rise to oscillations, but has an interesting effect to the bromate-malonic acid-sulfuric acid-NiL]2+ oscillation system (the period and the amplitudes of oscillating waves being varied). The oscillation trajectories of the potential of Br-selective electrodes vs. those of Pt electrodes are spiral instead of limit cycles. The domains of the existence of the oscillations were determine The influence of Br-, I-, Ag+, acrylamide, acetonitrile, or H2O2 on the oscillations was also investigated.