KINETICS AND MECHANISMS OF OXIDATIONS BY METAL-IONS .17. OXIDATION OF FORMATE ION BY ALKALINE OSMIUM-TETROXIDE

被引：0

作者：

VISHNOI, M ^{[1
]}

PRAKASH, A ^{[1
]}

MEHROTRA, RN ^{[1
]}

机构：

[1] JNV UNIV,DEPT CHEM,JODHPUR 342005,RAJASTHAN,INDIA

来源：

TRANSITION METAL CHEMISTRY | 1995年 / 20卷 / 02期

关键词：

D O I：

暂无

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The oxidation of formate ion by alkaline osmium tetroxide, such that [HCO2-] much greater than [Os-VIII], exhibits first-order dependence in [Os-VIII], an order less than unity in [HCO2-], and zero-order in [OH-]. HCO2- reacts as an ion-pair formed with an alkali metal ion and [OsO4(OH)(2)](2-) is the reactive species of Os-VIII. The formation of an intermediate Os-VIII-HCO(2)M complex is substantiated by the rapid-scan spectra of the reaction mixture. Anions (Cl-, ClO4-) have no effect on the rate. The close agreement between the observed k(H)/k(D) = 7.1 and the theoretically calculated value (7.0), based on the stretching frequencies of C-H and C-D bonds in the free molecule, indicates an outer-sphere mechanism.

引用

页码：208 / 211

页数：4

共 26 条

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