Synthesis of a copper-supported triplet nitrene complex pertinent to copper-catalyzed amination

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 ligan...

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Published in:Science (American Association for the Advancement of Science) 2019-09, Vol.365 (6458), p.1138-1143
Main Authors: Carsch, Kurtis M, DiMucci, Ida M, Iovan, Diana A, Li, Alex, Zheng, Shao-Liang, Titus, Charles J, Lee, Sang Jun, Irwin, Kent D, Nordlund, Dennis, Lancaster, Kyle M, Betley, Theodore A
Format: Article
Language:English
Subjects:
Absorption spectroscopy
Alkanes
Amination
Aromatic compounds
Catalysis
Chemical bonds
Coordination compounds
Copper
Copper compounds
Electron states
Intermediates
Nitrogen
Nitrogen compounds
Organic chemistry
Organic compounds
Quantum chemistry
X ray absorption
X-ray absorption spectroscopy
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Summary: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.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.aax4423