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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Global and Local Reactivity and Activation Patterns of HOOX (X = H, NO_2, CO_2~-, SO_3~-) Peroxides with Solvent Effects
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Global and Local Reactivity and Activation Patterns of HOOX (X = H, NO_2, CO_2~-, SO_3~-) Peroxides with Solvent Effects

机译：具有溶剂效应的过氧化物HOOX（X = H，NO_2，CO_2〜-，SO_3〜-）的整体和局部反应性和活化方式

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A detailed analysis of the global and local reactivity patterns of neutral and charged peroxides, including hydrogen peroxide (HOOH), peroxynitric acid (HOONO_2), the peroxymonocarbonic ion (HOOCO_2~-), and the peroxymonosulfate ion (HOOSO_3~-) in the presence of a polar solvent (water) is presented. The polar solvent effects are included using an isodensity surface polarized continuum model (IPCM). The (1,2) hydrogen-shift reaction for these peroxides is studied. The transition states involved in the (1,2) hydrogen shift have been located and characterized at the B3LYP/6-311G** level of theory. The global analysis shows that, although the replacement of one hydrogen atom in HOOH by a neutral NO_2 group enhances both the global softness and global electrophilicity, the substitution of one hydrogen atom by charged CO_2~- and SO_3~- groups results in a significant electrophilic deactivation of HOOCO_2~- and a moderate electrophilic activation of HOOSO_3~-. This result is observed in both the ground state and in some activated forms involved in the (1,2) hydrogen rearrangement. The local analysis, however, shows that the transition-state structures for the same rearrangement of HOOH and the HOOCO_2~- ion display an electrophilicity-enhanced pattern at the oxygen atom that is being deprotonated, thereby suggesting that this activated form is more likely to be involved in the oxygen-transfer reactions. The site-activation analysis performed on the basis of the variations in local softness from the ground to the transition states is also consistent with this local reactivity picture.
机译：详细分析中性和带电过氧化物的全局和局部反应模式，包括过氧化氢（HOOH），过氧硝酸（HOONO_2），过氧一碳酸根离子（HOOCO_2〜-）和过氧一硫酸根离子（HOOSO_3〜-）介绍了一种极性溶剂（水）。使用等密度表面极化连续介质模型（IPCM）包括极性溶剂效应。研究了这些过氧化物的（1,2）氢转移反应。 （1,2）氢转移所涉及的过渡态已被定位并表征为B3LYP / 6-311G **理论水平。整体分析表明，尽管HOOH中的一个氢原子被中性NO_2取代既增强了整体柔软性，又增强了整体亲电性，但一个带氢的CO_2〜-和SO_3〜-取代了一个氢原子却导致了显着的亲电性HOOCO_2〜-的失活和HOOSO_3〜-的中等亲电活化。在基态和参与（1,2）氢重排的某些活化形式中均观察到该结果。然而，局部分析表明，对于相同的HOOH和HOOCO_2-离子的重排，过渡态结构在被去质子化的氧原子上显示出亲电性增强的模式，从而表明该活化形式更可能参与氧转移反应。基于从地面到过渡态的局部柔软度的变化进行的位点活化分析也与此局部反应性图片一致。

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