REACTIONS OF SINGLET OXYGEN WITH ORGANOMETALLIC COMPLEXES .2. FORMATION OF A METASTABLE RHODIUM-DIOXYGEN COMPLEX

被引：21

作者：

SELKE, M ^{[1
]}

FOOTE, CS ^{[1
]}

KARNEY, WL ^{[1
]}

机构：

[1] UNIV CALIF LOS ANGELES,DEPT CHEM & BIOCHEM,LOS ANGELES,CA 90024

来源：

INORGANIC CHEMISTRY | 1993年 / 32卷 / 24期

关键词：

D O I：

10.1021/ic00076a001

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Photooxidation of the rhodium analogue of Vaska's complex (Rh(CO)Cl(PPh3)2, 1) at low temperature leads to the novel peroxo complex Rh(CO)Cl(PPh3)2O2 (2). The rate constant for combined physical and chemical interaction of singlet oxygen with 1 is (3.1 +/- 0.2) x 10(8) M-1 s-1 in CDC]3; that for chemical reaction alone is (1.2 +/- 0.5) x 10(8) M-1 s-1. Complex 2 is unstable at room temperature and rapidly loses dioxygen to re-form the starting material. Activation parameters for the decomposition are DELTAH(double dagger) = 23 +/- 2 kcal and DELTAS(double dagger) = 13 eu at 0-degrees-C.

引用

页码：5425 / 5426

页数：2

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