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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Reactivity of [1, 2-Benzisotellurazol-3(2H)-one] with Peroxynitrous Acid: Comparison with Ebselen Analogues
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Reactivity of [1, 2-Benzisotellurazol-3(2H)-one] with Peroxynitrous Acid: Comparison with Ebselen Analogues

机译：[1，2-Benzisotellurazol-3（2H）-one]与过氧亚硝酸的反应活性：与Ebselen类似物的比较

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摘要

The mechanism of the reaction of [1,2-benzisotellurazol-3(2H)-one], ebtellur derivative 2_Te, with peroxynitrous acid, HOONO, was elucidated at the density functional (B3LYP) level by using triple-ζ quality basis sets (BS1). It was found that in the gas phase the reaction, proceeding via the concerted pathway, occurs with ΔH = 0.3 (ΔG = (3.4)) kcal/mol HO-ONO bond cleavage barrier. The ΔG value of this barrier is only slightly larger than the (2.2) kcal/mol required for the HO-ONO bond homolysis. Inclusion of the solvent effects at the single-point PCM level increases the HO-ONO activation barrier to 5.8 kcal/mol. The product of the HO-ONO bond cleavage by 2_Te is the complex 2_Te(OH)(ONO), which could decay via two distinct pathways leading to NO_2 + 2_Te(OH) and 2_Te(O) + HONO. Both processes are endothermic in the gas phase: 23.7 (11.4) and 26.4 (14.5) kcal/mol, respectively. The inclusion of solvent effects makes the 2_Te(O) + HONO formation more favorable in water. The comparison of the reaction of 2_M + HOONO for M = Se and Te shows that the HO-ONO bond cleavage is fast for both metals, in the gas phase. However, the probability of competition in the concerted and stepwise pathways is higher for M = Te than for M = Se. The reaction of 2_Se with HOONO produces only selenoxide 2_Se(O), while the reaction of 2_Te with HOONO may produce the intermediate 2_Te(OH)(ONO) and 2_Te(O) + HONO. We also compared the mechanisms o the reactions of 2_Te with ONOO~- and HOONO.
机译：通过使用三重ζ质量基础集，阐明了[1,2-苯并异戊撑唑-3（2H）-one] ebtellur衍生物2_Te与过氧亚硝酸HOONO的反应机理（B3LYP）。 BS1）。发现在气相中，通过一致的途径进行的反应以ΔH＝ 0.3（ΔG＝（3.4））kcal / mol HO-ONO键裂解势垒发生。该势垒的ΔG值仅略大于HO-ONO键均质化所需的（2.2）kcal / mol。在单点PCM浓度下包含溶剂效应会将HO-ONO活化势垒提高到5.8 kcal / mol。 2_Te裂解HO-ONO键的产物是复合物2_Te（OH）（ONO），它可以通过两种不同的途径分解，生成NO_2 + 2_Te（OH）和2_Te（O）+ HONO。两种方法在气相中都是吸热的：分别为23.7（11.4）和26.4（14.5）kcal / mol。包含溶剂效应使2_Te（O）+ HONO的形成在水中更加有利。 2_M + HOONO对M = Se和Te的反应的比较表明，在气相中，两种金属的HO-ONO键裂解都很快。但是，M = Te比M = Se协调和逐步竞争的可能性更高。 2_Se与HOONO的反应仅生成硒氧化物2_Se（O），而2_Te与HOONO的反应则可能生成中间体2_Te（OH）（ONO）和2_Te（O）+ HONO。我们还比较了2_Te与ONOO〜-和HOONO反应的机理。

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