Zardi P, Pozzoli A, Ferretti F, Manca G, Mealli C, Gallo E
Department of Chemistry, University of Milan, Via Golgi 19, I-20133 Milan, Italy.
Dalton Trans. 2015 Jun 14;44(22):10479-89. doi: 10.1039/c5dt00951k.
A mechanism for the aziridination of olefins by aryl azides (ArN3), promoted by ruthenium(ii) porphyrin complexes, is proposed on the basis of kinetic and theoretical studies. All the recorded data support the involvement of a mono-imido ruthenium complex as the active intermediate in the transfer of the nitrene moiety "ArN" to the olefin. The selectivity of the aziridination vs. the uncatalysed triazoline formation can be enhanced by fine-tuning the electronic features of the porphyrin ligand and the olefin/azide catalytic ratio. The DFT study highlights the importance of an accessible triplet ground state of the intermediate ruthenium mono-imido complex to allow the evolution of the aziridination process.
基于动力学和理论研究，提出了一种由钌（II）卟啉配合物促进的芳基叠氮化物（ArN₃）对烯烃进行氮杂环丙烷化的机理。所有记录的数据都支持单亚氨基钌配合物作为将氮烯部分“ArN”转移到烯烃的活性中间体。通过微调卟啉配体的电子特性以及烯烃/叠氮化物的催化比例，可以提高氮杂环丙烷化相对于未催化的三唑啉形成的选择性。密度泛函理论（DFT）研究突出了中间体钌单亚氨基配合物可及的三重基态对氮杂环丙烷化过程进展的重要性。
