González-Navarrete Patricio, Sensato Fabricio R, Andrés Juan, Longo Elson
Institute of Chemistry, São Paulo State University, Interdisciplinary Laboratory of Electrochemistry and Ceramics , Francisco Degni 55, Araraquara 14800-900, Brazil.
J Phys Chem A. 2014 Aug 7;118(31):6092-103. doi: 10.1021/jp504172g. Epub 2014 Jul 28.
In this research, a comprehensive theoretical investigation has been conducted on oxygen atom transfer (OAT) reactions from Mimoun complexes to sulfides and sulfoxides. The joint use of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool to analyze the evolution of chemical events along a reaction pathway. The progress of the reaction has been monitored by structural stability domains from ELF topology while the changes between them are controlled by turning points derived from CT which reveal that the reaction mechanism can be separated in several steps: first, a rupture of the peroxo O1-O2 bond, then a rearrangement of lone pairs of the sulfur atom occurs and subsequently the formation of S-O1 bond. The OAT process involving the oxidation of sulfides and sulfoxides is found to be an asynchronous process where O1-O2 bond breaking and S-O1 bond formation processes do not occur simultaneously. Nucleophilic/electrophilic characters of both dimethyl sulfide and dimethyl sulfoxide, respectively, are sufficiently described by our results, which hold the key to unprecedented insight into the mapping of electrons that compose the bonds while the bonds change.
在本研究中，对从米蒙配合物到硫化物和亚砜的氧原子转移（OAT）反应进行了全面的理论研究。电子定位函数（ELF）和托姆突变理论（CT）的联合使用为分析化学反应过程中化学事件的演变提供了有力工具。反应进程通过ELF拓扑结构的结构稳定性域进行监测，而它们之间的变化则由CT导出的转折点控制，这表明反应机理可分为几个步骤：首先，过氧O1 - O2键断裂，然后硫原子孤对电子重排，随后形成S - O1键。发现涉及硫化物和亚砜氧化的OAT过程是一个异步过程，其中O1 - O2键断裂和S - O1键形成过程不同时发生。我们的结果充分描述了二甲基硫醚和二甲基亚砜各自的亲核/亲电特性，这是深入了解键变化时构成键的电子映射的关键。
