Kurtis M Carsch1, Ida M DiMucci2, Diana A Iovan1, Alex Li1, Shao-Liang Zheng1, Charles J Titus3, Sang Jun Lee4, Kent D Irwin3,5, Dennis Nordlund4, Kyle M Lancaster6, Theodore A Betley7. 1. Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA. 2. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA. 3. Department of Physics, Stanford University, Stanford, CA, USA. 4. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USA. 5. SLAC National Accelerator Laboratory, Menlo Park, CA, USA. 6. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA. betley@chemistry.harvard.edu kml236@cornell.edu. 7. Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA. betley@chemistry.harvard.edu kml236@cornell.edu.
Abstract
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.
Terminal copper-nitrenoidn class="Chemical">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) dinitrogencomplex bearing a sterically encumbered dipyrrin ligand to produce terminal copper nitrenecomplexes 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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