Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin, Germany.
Angew Chem Int Ed Engl. 2012 Jun 4;51(23):5544-55. doi: 10.1002/anie.201108363. Epub 2012 Mar 16.
Hydrogen-atom transfer (HAT), as one of the fundamental reactions in chemistry, is investigated with state-of-the-art gas-phase experiments in conjunction with computational studies. The focus of this Minireview concerns the role that the intrinsic properties of gaseous oxo-clusters play to permit HAT reactivity from saturated hydrocarbons at ambient conditions. In addition, mechanistic implications are discussed which pertain to heterogeneous catalysis. From these combined experimental/computational studies, the crucial role of unpaired spin density at the abstracting atom becomes clear, in distinct contrast to recent conclusions derived from solution-phase experiments.
氢原子转移（HAT）作为化学反应的基本反应之一，通过最先进的气相实验与计算研究进行了研究。这篇综述的重点是探讨气态氧簇的固有特性在室温条件下允许饱和烃发生 HAT 反应的作用。此外，还讨论了与多相催化相关的机理影响。通过这些组合的实验/计算研究，在抽象原子上的不成对自旋密度的关键作用变得清晰，与最近从溶液相实验得出的结论形成鲜明对比。
