Characterization and Reactivity Studies of a Terminal Copper-Nitrene Species

Text Complet
CharacterizationReactivity-EnglishEdition.pdf closed access CharacterizationReactivity-GermanEdition.pdf closed access
Sol·licita còpia a l'autor de l'article
En omplir aquest formulari esteu demanant una còpia de l'article dipositat al repositori institucional (DUGiDocs) al seu autor o a l'autor principal de l'article. Serà el mateix autor qui decideixi lliurar una còpia del document a qui ho sol•liciti si ho creu convenient. En tot cas, la Biblioteca de la UdG no intervé en aquest procés ja que no està autoritzada a facilitar articles quan aquests són d'accés restringit.
Compartir
High-valent terminal copper–nitrene species have been postulated as key intermediates in copper-catalyzed aziridination and amination reactions. The high reactivity of these intermediates has prevented their characterization for decades, thereby making the mechanisms ambiguous. Very recently, the Lewis acid adduct of a copper–nitrene intermediate was trapped at −90 °C and shown to be active in various oxidation reactions. Herein, we describe for the first time the synthesis and spectroscopic characterization of a terminal copper(II)–nitrene radical species that is stable at room temperature in the absence of any Lewis acid. The azide derivative of a triazamacrocyclic ligand that had previously been utilized in the stabilization of aryl–CuIII intermediates was employed as an ancillary ligand in the study. The terminal copper(II)–nitrene radical species is able to transfer a nitrene moiety to phosphines and abstract a hydrogen atom from weak C−H bonds, leading to the formation of oxidized products in modest yields ​
​Tots els drets reservats