MOLECULAR-OXYGEN, SUPEROXIDE, AND PEROXIDE AS LIGANDS IN A CON5 COMPLEX

被引：13

作者：

MAEDER, M ^{[1
]}

MACKE, HR ^{[1
]}

机构：

[1] UNIV HOSP BASEL,INST NUCL MED,CH-4031 BASEL,SWITZERLAND

来源：

INORGANIC CHEMISTRY | 1994年 / 33卷 / 14期

关键词：

D O I：

10.1021/ic00092a020

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The cobalt(II) complex (papd)CoII(H2O)2+ (papd = 1,5,8,11,15-pentaazapentadecane) reacts with molecular oxygen to form mu-peroxo complex in the traditional Wilkins reaction scheme (k1 = 1.4 x 10(7) M-1 s-1, k-1 = 0.65 s-1, k2 = 1.2 X 10(7) M-1 s-1, k-2 = 2.24 x 10-6 s-1). Formation equilibrium constants are 2.2 X 10(7) M-1 and 1.2 x 10(20) M-2 for the superoxo and peroxo complexes. The absorption spectra of the intermediate mononuclear superoxo complex and the mu-peroxo complex are very similar. Characterization of the (papd)Co(II)H2O)2+ precursor, 4T1g(O(h)), pK(a)((papd)Co(H2O/OH)2+/+) = 12.6, E-degrees((papd)Co(H2O)3+/2+) = 0.05 V, allows the calculation of the ligating properties of the superoxide and peroxide ions toward (papd)Co(II)(H2O)3+, K((papd)Co(III)(H2O)3+ + O2-) = 10(12) M-1 and K(2(papd)Co(III)(H2O)3+ + O2(2-)) = 2 x 10(37) M-2.

引用

页码：3135 / 3140

页数：6

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