KINETICS AND MECHANISM OF OXIDATION OF COBALT(II) MACROCYCLES BY IODINE, BROMINE, AND HYDROGEN-PEROXIDE

被引:58
作者
HECKMAN, RA
ESPENSON, JH
机构
[1] US DOE,AMES LAB,AMES,IA 50011
[2] IOWA STATE UNIV,DEPT CHEM,AMES,IA 50011
关键词
D O I
10.1021/ic50191a007
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A series of cobalt(II) complexes of tetradehtate, 14-membered macrocyclic ligands with nitrogen donor atoms is oxidized by bromine and iodine in acidic aqueous solution to the corresponding monohalocobalt(III) product. The rate law shows a first-order dependence on each reactant; rate constants and reduction potentials were determined for each substance. Only one of the cobalt(II) complexes, CoII([14]aneN4)2+, reacts with hydrogen peroxide in the same manner, and in that reaction positive results were obtained in scavenging for a hydroxyl radical intermediate. The other peroxide reactions apparently do not produce HO. The mechanisms of all of the reactions are considered and discussed. © 1979, American Chemical Society. All rights reserved.
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页码:38 / 43
页数:6
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