HYDROXIDE-INDUCED SYNTHESIS OF THE SUPEROXIDE ION FROM DIOXYGEN AND ANILINE, HYDROXYLAMINE, OR HYDRAZINE

被引：15

作者：

JEON, SW ^{[1
]}

SAWYER, DT ^{[1
]}

机构：

[1] TEXAS A&M UNIV SYST,DEPT CHEM,COLLEGE STN,TX 77843

来源：

INORGANIC CHEMISTRY | 1990年 / 29卷 / 23期

关键词：

D O I：

10.1021/ic00348a007

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

With dioxygen-saturated (1 atm, 2.1 mM) dimethyl sulfoxide solutions that contain aniline (1–15 mM), the addition of excess hydroxide ion (10:1 -OH/PhNH2) yields approximately two superoxide ions (O2#x2212;), one azobenzene, and one hydrogen peroxide per two aniline molecules (2PhNH2+ 2-OH + 302→ 202-+ PhN=NPh + HOOH + 2H20). Similar stoichiometries and yields of 02-are achieved with the N-substituted anilines; the relative reaction rates are in the order PhNHNH2> PhNHPh > PhNHMe > PhNH2. The apparent yield of 02-is low when PhNHNH2is the substrate, because the latter reduces 02-to HOO-. With hydroxylamines and excess -OH, dioxygen is reduced to 02-(2H2NOH + 4O2+ 4-OH > 2O2-+ HOOH + 2NO2-;+ 4H2O), but the yield is low because O2-reacts with excess H2NOH to give NO and HOO-. Although the combination of H2NNH2, O2, and -OH is unreactive the addition of anthraquinone (AQ) or its ethyl derivative (EtAQ) catalyzes the stoichiometric production of O2-(H2NNH2+ 4O2+ 4-OH EtAO →4O2-+ N2+ 4H2O). Mechanisms are proposed for the substrate/-OH reduction of O2via electron-transfer steps. © 1990, American Chemical Society. All rights reserved.

引用

页码：4612 / 4615

页数：4

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