AM1-SM2 calculations model the redox potential of nitroxyl radicals such as TEMPO

被引：63

作者：

Rychnovsky, SD ^{[1
]}

Vaidyanathan, R ^{[1
]}

Beauchamp, T ^{[1
]}

Lin, R ^{[1
]}

Farmer, PJ ^{[1
]}

机构：

[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1999年 / 64卷 / 18期

关键词：

D O I：

10.1021/jo990636c

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Nitroxyl radicals can be oxidized to N-oxo ammonium salts that are themselves useful oxidants for primary and secondary alcohols. Several computational methods were investigated in order to predict the redox potential of nitroxyl radicals and to better understand the behavior of different nitroxides as catalysts for alcohol oxidation. The difference in calculated heats of formation for N-oxo ammonium ions and nitroxyl radicals using AM1 did not lead to a useful correlation with experimental redox potential as measured by cyclic voltammetry. However, when both the N-oxo ammonium ion and the nitroxyl radical were evaluated using the Cramer-Truhlar solvation model (SM2), a linear correlation was observed between the difference in heats of formation and the experimental redox values. This correlation may be used to correctly predict the redox potential of new nitroxyl radicals.

引用

页码：6745 / 6749

页数：5

共 33 条

[21] OXOAMMONIUM SALTS .5. A NEW SYNTHESIS OF HINDERED PIPERIDINES LEADING TO UNSYMMETRICAL TEMPO-TYPE NITROXIDES - SYNTHESIS AND ENANTIOSELECTIVE OXIDATIONS WITH CHIRAL NITROXIDES AND CHIRAL OXOAMMONIUM SALTS [J].