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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Effects of Aromatic Substitutions on the Photoreactions in Mg~(·+)(C_6H_nF_2X_(4-n)) (X = F, CH_3) Complexes: Formation and Decomposition of Benzyne Radical Cations
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Effects of Aromatic Substitutions on the Photoreactions in Mg~(·+)(C_6H_nF_2X_(4-n)) (X = F, CH_3) Complexes: Formation and Decomposition of Benzyne Radical Cations

机译：芳基取代对Mg〜（+）（C_6H_nF_2X_（4-n））（X = F，CH_3）配合物中光反应的影响：苯并自由基自由基的形成和分解

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Photoinduced reactions have been systematically studied on mass-selected complexes of Mg~(·+) with tri- and tetrasubstituted benzene by F and/or CH_3. The complexes fall into two groups. The Group I complexes involve bidentate coordination of the o-F atoms to Mg(·+), whereas the Group II complexes feature the linkage of Mg(·+) to only one of the F atoms. The o-benzyne radical cations were found to be the predominant photolysis products from the Group I complexes, but the yields of the benzyne radical cation products were low for Group II. For each group of complexes, different substituents, including CH_3 (medium σ-electron donor) and F (strong σ-electron acceptor and weak π-electron donor), affect the branching ratios significantly. For example, they result in different decomposition thresholds of the o-benzyne radical cations. Through the studies of aromatic substitution, the pathways for the formation and decomposition of o-benzyne radical cations have been brought to light. With the help of quantum mechanics calculations, the observed substitutent effects on the photoformation and decomposition of the o-benzyne radical cations are explained mainly from the energy point of view. We found that although o-benzyne radical cations are formed by the direct abstraction of the F atoms, the formation of m-benzyne radical cations is stepwise, involving a π-~+MgF intermediate.
机译：通过F和/或CH_3，对Mg〜（+）与三，四取代苯的质量选择配合物进行了系统的光诱导反应研究。复合物分为两组。 I类络合物涉及o-F原子与Mg（·+）的双齿配位，而II类络合物具有Mg（·+）仅与F个原子之一相连的特征。发现邻-苯甲酰基自由基阳离子是第一类配合物的主要光解产物，但是对于第二类，苯炔自由基阳离子产物的产率较低。对于每组配合物，不同的取代基（包括CH_3（中等σ电子给体）和F（强σ电子受体和弱π电子给体）会显着影响分支比。例如，它们导致邻-苄基自由基阳离子的分解阈值不同。通过对芳香族取代的研究，发现了邻-苄基自由基阳离子形成和分解的途径。借助量子力学计算，主要从能量的角度解释了观察到的取代基对邻苯并zy基自由基阳离子的光形成和分解的影响。我们发现，尽管邻-苄基自由基阳离子是通过F原子的直接提取形成的，但间-苄基自由基阳离子的形成是逐步的，涉及一个π-〜+ MgF中间体。

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