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首页> 外文会议>International Manuel M. Baizer Symposium >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-羟基氨基吡唑-2- in-5-羟基嘧啶电化学氧化的实验与理论研究

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摘要

The electrochemical oxidation of 1-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 B3L YP 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 (UB3L YP/6-31G~*//UB3LY YP/6-31G~*).
机译：1-R-3-甲基-4-羟基咪唑-2 in-5-羟基吡吡唑（R = H，C_6H_5，C_6H_4（4'BR），C_6H_3（2'-NO_2-4'-CF_3）的电化学氧化已经通过循环伏安法和电解在乙腈中研究了玻璃碳和铂电极，与ESR，AB Initio Rhf，RoHF和UHF（基于6-31g〜* - 6-311 ++ g〜**）以及B3L YP方法。单一电子转移导致在Z构型中形成Iminoxyls，随着介绍碱基的碱度的增加而显着降低了氧化电位。基础培养基中的N-H衍生物的基团进一步氧化至3-甲基-4-硝基吡咯烷唑-1- in-5-oon。通过AB Initio Commerio Compinulation计算，高血清耦合常数的实验值（G 2.0045，A_（N7）30.78-31.33，A_（n1）1.87-2.12）仅考虑电子相关效果（UB3L YP / 6-31G〜* // ub3ly yp / 6-31g〜*）。

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