Disproportionation of aquachromyl(IV) ion by hydrogen abstraction from coordinated water

被引：23

作者：

Nemes, A ^{[1
]}

Bakac, A ^{[1
]}

机构：

[1] Iowa State Univ, Ames Lab, Ames, IA 50011 USA

来源：

INORGANIC CHEMISTRY | 2001年 / 40卷 / 12期

关键词：

D O I：

10.1021/ic0013577

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

In aqueous solutions, the aquachromyl(IV) ion, CraqO2+, disproportionates to Cr-aq(3+) and HCrO4-. The reaction exhibits second-order kinetics with an inverse [H+] dependence, -d[CraqO2+]/dt = 38.8[CraqO2+](2)[H+](-1) at 25 degreesC. The combination of the rate law and substantial kinetic isotope effect, k(H)/k(D) = 6.9, suggests a mechanism whereby a hydrogen atom is abstracted from a coordinated molecule of water or hydroxo group within a singly deprotonated transition state. The buildup of chromate is more complicated and somewhat slower than the loss of chromyl, suggesting the involvement of intermediates.

引用

页码：2720 / 2724

页数：5