Abstract：
Excitation of photoactive electron donor-acceptor (EDA) complexes to generate radical is a promising approach in radical chemistry. In this study, we introduce a new model of H-bonding EDA complexes for the selective hydrothiolation and hydroxysulfenylation of carbonyl-activated alkenes with diverse thiols under visible light conditions. The reliability of this H-bonding EDA complex model has been confirmed by meticulous experimental and theoretical calculations. Mechanistic investigations have revealed the significant influence of the solvent in determining whether the excitation of photoactive H-bonding EDA complex leads to charge transfer (CT) or energy-charge transfer (En-CT), thereby controlling Markovnikov and anti-Markovnikov selectivity. Notably, the Quantum Theory of Atoms in Molecules (QTAIM) analysis clearly shows that the excited state of the C=O-H-S EDA complex involves closed-shell partially covalent interactions.
摘要：
激发光活性电子供体-受体（EDA）络合物以产生自由基是自由基化学中的一种有前途的方法。在这项研究中,我们介绍了一种新的H键EDA配合物模型，用于在可见光条件下羰基活化的烯烃与多种硫醇的选择性氢硫醇化和羟基亚磺酰化。这种H键EDA复杂模型的可靠性已通过细致的实验和理论计算得到证实。机理研究表明，溶剂在确定光敏H键EDA复合物的激发是否会导致电荷转移（CT）或能量-电荷转移（En-CT）方面具有重大影响，从而控制Markovnikov和反Markovnikov选择性。值得注意的是,分子中原子的量子理论（QTAIM）分析清楚地表明，C＝O---H-SEDA复合物的激发态涉及闭壳部分共价相互作用。
