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首页> 外文会议>Fifth International Manuel M.Baizer Symposium in Honor of Professor Jean Michel Saveant at the 201st Meeting of the Electrochemical Society Centennial Meeting May 12-17, 2002 Philadelphia, PA, USA >EXPERIMENTAL AND THEORETICAL STUDY OF ELECTROCHEMICAL OXIDATION OF 4-HYDROXYIMINOPYRAZOL-2-IN-5-ONES
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EXPERIMENTAL AND THEORETICAL STUDY OF ELECTROCHEMICAL OXIDATION OF 4-HYDROXYIMINOPYRAZOL-2-IN-5-ONES

机译：4-羟基亚氨基吡唑-2-in-5-ones电化学氧化的实验和理论研究

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摘要

The electrochemical oxidation of l-R-3-methyl-4-hydroxyiminopyrazol-2-in-5-ones (R = H, C_6H_5, C_6H_4(4′-Br), C_6H_3(2′-NO_2-4′-CF_3)) has been studied on glasscarbon and platinum electrodes in acetonitrile by cyclic voltammetry and electrolysis in combination with ESR, ab initio RHF, ROHF and UHF (bases 6-31 G~* - 6-311++G~**) as well as by B3LYP method. Single electron transfer results in formation of iminoxyl radicals in Z-configuration, oxidation potentials being significantly reduced with the increase of the basicity of the introduced bases. The radical of N-H derivative in basic medium is oxidized further to 3-methyl-4-nitroso-pyrazol-1-in-5-one. Experimental values of hyperfine coupling constants (g 2.0045, a_(N7) 30.78-31.33, a_(N1) 1.87-2.12) are reproduced by ab initio calculation only if electron correlation effects are taken into account (UB3LYP/6-31G~*//UB3LYP/6-31G~*).
机译：1R-3-甲基-4-羟基亚氨基吡唑-2-in-5-ones（R = H，C_6H_5，C_6H_4（4'-Br），C_6H_3（2'-NO_2-4'-CF_3））的电化学氧化通过循环伏安法和电解结合ESR，从头开始的RHF，ROHF和UHF（碱6-31 G〜*-6-311 ++ G〜**）以及B3LYP在乙腈中的玻璃碳和铂电极上进行了研究方法。单电子转移导致形成Z构型的亚氨基氧基，随着引入碱的碱度的增加，氧化电位显着降低。在碱性介质中，N-H衍生物的基团被进一步氧化为3-甲基-4-亚硝基-吡唑-1-合-5-酮。仅在考虑电子相关效应的情况下，通过从头算来复制超精细耦合常数（g 2.0045，a_（N7）30.78-31.33，a_（N1）1.87-2.12）的实验值（UB3LYP / 6-31G〜* / / UB3LYP / 6-31G〜*）。

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