Characterization and Reactivity Studies of a Terminal Copper-Nitrene Species

Full Text
CharacterizationReactivity-EnglishEdition.pdf embargoed access CharacterizationReactivity-GermanEdition.pdf embargoed access
Request a copy
When filling the form you are requesting a copy of the article, that is deposited in the institutional repository (DUGiDocs), at the autor or main autor of the article. It will be the same author who decides to give a copy of the document to the person who requests it, if it considers it appropriate. In any case, the UdG Library doesn’t take part in this process because it is not authorized to provide restricted articles.
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