Castiñeira Reis Marta, Marín-Luna Marta, Silva López Carlos, Faza Olalla Nieto
Departamento de Quı́mica Orgánica, Universidade de Vigo , Lagoas-Marcosende, 36310 Vigo, Spain.
Departamento de Quı́mica Orgánica, Universidade de Vigo , Campus As Lagoas, 32004 Ourense, Spain.
Inorg Chem. 2017 Sep 5;56(17):10570-10575. doi: 10.1021/acs.inorgchem.7b01529. Epub 2017 Aug 22.
Density functional theory is applied to the study of the oxygen atom transfer reaction from sulfoxide (DMSO) to phosphine (PMe) catalyzed by the [MoO] active core. In this work, two fundamentally different roles are explored for this dioxometal complex in the first step of the catalytic cycle: as an oxidizing agent and as a Lewis acid. The latter turns out to be the favored pathway for the oxygen atom transfer. This finding may have more general implications for similar reactions catalyzed by the same [MoO] core.
密度泛函理论被应用于研究由[MoO]活性核催化的从亚砜（二甲基亚砜）到膦（三甲基膦）的氧原子转移反应。在这项工作中，探索了这种二氧金属配合物在催化循环第一步中的两种根本不同的作用：作为氧化剂和作为路易斯酸。结果表明，后者是氧原子转移的有利途径。这一发现可能对由相同[MoO]核催化的类似反应具有更普遍的意义。
