ACID DISSOCIATION KINETICS OF THE COPPER(II) COMPLEX OF A 15-MEMBERED MIXED N3O2 DONOR MACROCYCLE

被引：8

作者：

HAY, RW ^{[1
]}

HASSAN, MM ^{[1
]}

FENTON, DE ^{[1
]}

MURPHY, BP ^{[1
]}

机构：

[1] UNIV SHEFFIELD,DEPT CHEM,SHEFFIELD S3 7HF,S YORKSHIRE,ENGLAND

来源：

TRANSITION METAL CHEMISTRY | 1994年 / 19卷 / 05期

关键词：

D O I：

10.1007/BF00136374

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The kinetics of the acid dissociation of the copper(II) complex of the 15-membered N3O2 donor macrocycle [prepared by reaction of 2,6-bis(2-aminophenoxymethyl)-pyridine with glyoxal in the presence of a manganese(II) template followed by reduction of the two imine linkages with NaBH4] was studied over an acidity range (0.01 - 0.5 mol dm(-3) [H+]) at 25 degrees C and I = 1.0 mol dm(-3) by stopped-flow methods. A biphasic reaction was observed at 752 nm, the first reaction being complete within 20 ms at 25 degrees C and too rapid to study in detail. The second reaction shows a good first order dependence on the hydrogen ion concentration over the whole acidity range and kobs = k(0) + k(H)[H+], where k(0) = 0.52 s(-1) and k(H) = 40.2 dm(3) mol(-1) s(-1) at 25 degrees C. The k(0) term represents a small but significant solvolytic reaction. The mechanism of the acid-catalysed dissociation is discussed.

引用

页码：559 / 560

页数：2

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