NaBrO_3-CH_2(COOH)_2-H_3PO_4-CuL^(2+)体系的振荡化学研究

Oscillating Chemistry of NaBrO_3-CH_2(COOH)_2-H_PO_4-CuL^(2+)System

四氮杂大环配合物是生物体内一些金属酶结构单元的模拟物,可作为振荡反应催化剂来加以研究.我们报道的一些四氮杂大环铜(Ⅱ)、镍(Ⅱ)配合物所参与的催化振荡反应体系中采用的底液都是稀H_2SO_4,尚未见以H_3PO_4作底液的报道。

We investigated the oscillating chemical reaction of NaBrO3-CH2 (COOH)2-CuL2+-H3PO4 system, where [CuL2+] is [Cu(Me6[l4]-4,11-dieneN1](ClO4)2 · 3H2O. The domain of the existance of the oscillation was obtained in the coordinates of NaBrO3 and CH2(COOH)2. The effects of initial concentration of the components on the oscillation were studied. Various re-ductants (HOOCCOOH, Vcetc ) can influence the oscillations. So HBrO2 is an important intermediate. When Ag+, Hg2+(4× 10-5 mol/L) were added to the oscillating system, the oscillations were quenched immediately. It seems that Br- plays the role of a control intermediate as in B-Z system catalyzed by Ce4+ or Mn2+, In this system, the oscillations were also inhibited by acrylamide, H2O2 etc. This shows that the free radical may be involved in the reaction process.