Zeppilli Davide, Madabeni Andrea, Sancineto Luca, Bagnoli Luana, Santi Claudio, Orian Laura
Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova, Italy.
Gruppo di Catalisi Sintesi e Chimica Organica Verde Dipartimento di Scienze Farmaceutiche, Università degli Studi di Perugia, Via del Liceo 1, 06122 Perugia, Italy.
Inorg Chem. 2023 Oct 23;62(42):17288-17298. doi: 10.1021/acs.inorgchem.3c02568. Epub 2023 Sep 28.
PhSeZnCl, which is also known as Santi's reagent, can catalyze the reduction of hydrogen peroxide by thiols with a GPx-like mechanism. In this work, the first step of this catalytic cycle, i.e., the reduction of HO by PhSeZnCl, is investigated using state-of-the-art density functional theory calculations. Then, the role of the metal is evaluated by replacing Zn with its group 12 siblings (Cd and Hg). The thermodynamic and kinetic factors favoring Zn are elucidated. Furthermore, the role of the halogen is considered by replacing Cl with Br in all three metal compounds, and this turns out to be negligible. Finally, the overall GPx-like mechanism of PhSeZnCl and PhSeZnBr is discussed by evaluating the energetics of the mechanistic path leading to the disulfide product.
PhSeZnCl，也被称为桑蒂试剂，能够通过类似于谷胱甘肽过氧化物酶（GPx）的机制催化硫醇对过氧化氢的还原反应。在本研究中，利用最先进的密度泛函理论计算方法，对该催化循环的第一步，即PhSeZnCl对HO的还原反应进行了研究。然后，通过用第12族的同族元素（镉和汞）取代锌来评估金属的作用。阐明了有利于锌的热力学和动力学因素。此外，在所有三种金属化合物中用溴取代氯来考虑卤素的作用，结果发现其作用可忽略不计。最后，通过评估生成二硫产物的机理路径的能量学，讨论了PhSeZnCl和PhSeZnBr类似GPx的整体机制。
