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Electron capture by the thiyl radical and disulfide bond: Ligand effects on the reduction potential

机译：巯基自由基和二硫键捕获电子：配体对还原电位的影响

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摘要

The effect of non-polar and polar ligands and of monovalent cations on the one-electron reduction potential of the thiyl radical and the disulfide bond was evaluated. The reduction potentials E8 for the CH_3SC-nL/ CH _3S--nL and CH_3SSCH_3-L/ CH _3SSCH_3C--L redox couples were calculated at the B_3LYP, M06-2X and MP2 levels of theory, with n=1, 2 and L=CH _4, C_2H_4, H_2O, CH_3OH, NH_3, CH_3COOH, CH_3CONH_2, NH 4+, Na+, K+ and Li+. Non-polar ligands decrease the E8 value of the thiyl radical and disulfide bond, while neutral polar ligands favour electron uptake. Charged polar ligands and cations favour electron capture by the thiyl radical while disfavouring electron uptake by the disulfide bond. Thus, the same type of ligand can have a different effect on E8 depending on the redox couple. Therefore, properties of an isolated ligand cannot uniquely determine E8. The ligand effects on E are discussed in terms of the vertical electron affinity and reorganization energy, as well as molecular orbital theory. For a given redox couple, the ligand type influences the nature of the anion formed upon electron capture and the corresponding reorganization process towards the reduced geometry.
机译：评估了非极性和极性配体以及一价阳离子对噻吩基和二硫键的单电子还原电势的影响。 CH_3SC-nL / CH _3S--nL和CH_3SSCH_3-L / CH _3SSCH_3C--L氧化还原对的还原电势E8是在理论上的B_3LYP，M06-2X和MP2水平上计算的，其中n = 1、2和L = CH _4，C_2H_4，H_2O，CH_3OH，NH_3，CH_3COOH，CH_3CONH_2，NH 4 +，Na +，K +和Li +。非极性配体降低了巯基和二硫键的E8值，而中性极性配体则有利于电子吸收。带电的极性配体和阳离子有利于硫基自由基捕获电子，同时不利于二硫键吸收电子。因此，取决于氧化还原对，相同类型的配体对E8的影响可能不同。因此，分离的配体的性质不能唯一确定E8。根据垂直电子亲和力和重组能以及分子轨道理论讨论了配体对E的影响。对于给定的氧化还原对，配体类型会影响电子捕获后形成的阴离子的性质以及相应的重组过程，从而降低几何形状。

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