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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Combined Experimental and Theoretical Studies on the Radical Nucleophile Addition Reaction for Sulfide- and Selenide-Centered Anions
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Combined Experimental and Theoretical Studies on the Radical Nucleophile Addition Reaction for Sulfide- and Selenide-Centered Anions

机译：硫化物和硒固定阴离子自由基亲核试剂加成反应的组合实验与理论研究

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摘要

The reactivity of sulfur- and selenium-centered nucleophiles toward 1-naphthyl radicals was studied in dimethylsulfoxide. The photo-stimulated reaction of sulfide anions, -SC(NH)C6H3 (1), -SC(NH)NH2 (2), and -SC(NH)CH3 (3), renders, after the addition of MeI, methyl 1-naphthylsulfide as a main product together with bis(1-naphthyl) sulfide and naphthalene under irradiation. Concordantly, the reaction of selenide anions, -SeC(NH)C6H3 (4), -SeC(NH)NH2 (5), and -SeCN (6), produces methyl 1-naphthyl selenide, bis(1-naphthyl) selenide, and naphthalene in the presence of potassium tert-butoxide anion (entrainment conditions). Absolute rate constants for the coupling of ions 1-6 to 1-naphthyl radicals were determined; as a general trend, the selenide-centered nucleophiles enhance in 2 times the reactivity of their sulfide analogues. From the mechanistic study, it is proposed that the unstable radical anion produced by the addition of the nucleophile to 1-naphthyl radical affords, after fragmentation, 1-naphthylsulfide/selenide anion. In addition, experimental results are discussed in terms of density functional theory calculations. There is a generally good agreement between the experimental and the calculated reactivities, the spin density being the main parameter to describe the difference found among the anions under study. Moreover, the calculations predict that anion -SeC(NH)CH3 (7) would be a good candidate for the synthesis of selenide derivatives.
机译：在二甲基磺酰甲醚中研究了硫 - 和硒中心亲核试剂的反应性朝向1-萘基。硫化物阴离子，-SC（NH）C6H3（1），-SC（NH）NH 2（2）和-SC（NH）CH3（3），呈添加后，甲基1的呈照片刺激反应 - 作为主要产物与双（1-萘基）硫化物和氧乙烯在照射下。一致地，硒化物阴离子，-Sec（NH）C6H3（4），-SEC（NH）NH 2（5）和-Secn（6）的反应产生甲基1-萘基硒化醇，BIS（1-萘基）硒化烷烃，在叔丁醇钾阴离子（夹带条件）存在下萘。确定离子1-6至1-萘基的偶联的绝对速率常数;作为一般趋势，硒化硒化亲核试剂增强了其硫化物类似物的反应性的2倍。从机械研究中，提出通过加入亲核试剂产生的不稳定的自由基阴离子，在碎片，1-萘基/硒化物阴离子之后提供给1-萘基。此外，在密度泛函理论计算方面讨论了实验结果。实验和计算的反应性之间存在一般良好的一致性，旋转密度是描述在研究中的阴离子中发现的差异的主要参数。此外，计算预测阴离子-SEC（NH）CH 3（7）是合成硒化衍生物的良好候选者。

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