Terminal copper-nitrenoid complexes have inspired interest in their fundamental bonding structures as well as their putative intermediacy in catalytic nitrene-transfer reactions. Here, we report that aryl azides react with a copper(I) dinitrogen complex bearing a sterically encumbered dipyrrin ligand to produce terminal copper nitrene complexes with near-linear, short copper-nitrenoid bonds [1.745(2) to 1.759(2) angstroms]. X-ray absorption spectroscopy and quantum chemistry calculations reveal a predominantly triplet nitrene adduct bound to copper(I), as opposed to copper(II) or copper(III) assignments, indicating the absence of a copper-nitrogen multiple-bond character. Employing electron-deficient aryl azides renders the copper nitrene species competent for alkane amination and alkene aziridination, lending further credence to the intermediacy of this species in proposed nitrene-transfer mechanisms.
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Characterization and Reactivity Studies of a Terminal Copper-Nitrene SpeciesT Corona et al. Angew Chem Int Ed Engl 55 (45), 14005-14008. PMID 27723252.High-valent terminal copper-nitrene species have been postulated as key intermediates in copper-catalyzed aziridination and amination reactions. The high reactivity of th …
Bonding and Structure of Copper NitrenesTR Cundari et al. Inorg Chem 47 (21), 10067-72. PMID 18834113.Copper nitrenes are of interest as intermediates in the catalytic aziridination of olefins and the amination of C-H bonds. However, despite advances in the isolation and …
Isolation of Bridging and Terminal Coinage Metal-Nitrene ComplexesF Dielmann et al. J Am Chem Soc 136 (10), 3800-2. PMID 24559041.Transition metal complexes featuring a metal-nitrogen multiple bond have been widely studied due to their implication in dinitrogen fixation and catalytic nitrogen-carbon …
Recent Progress on Cyclic Nitrenoid Precursors in Transition-Metal-Catalyzed Nitrene-Transfer ReactionsT Shimbayashi et al. Chemistry 25 (13), 3156-3180. PMID 30183111. - ReviewNitrene-transfer reactions are powerful synthetic tools for the direct incorporation of nitrogen atoms into organic molecules. The discovery of novel nitrene-transfer rea …
[CuO](+) and [CuOH](2+) Complexes: Intermediates in Oxidation Catalysis?N Gagnon et al. Acc Chem Res 48 (7), 2126-31. PMID 26075312. - ReviewCharacterization of monocopper intermediates in enzymes and other catalysts that attack strong C-H bonds is important for unraveling oxidation catalysis mechanisms and, u …
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Ligand Redox Noninnocence in [Co III(TAML)] 0/- Complexes Affects Nitrene FormationNP van Leest et al. J Am Chem Soc 142 (1), 552-563. PMID 31846578.The redox noninnocence of the TAML scaffold in cobalt-TAML (tetra-amido macrocyclic ligand) complexes has been under debate since 2006. In this work, we demonstrate with …