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) Vol. 365; no. 6458; p. 1138 |
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| Main Authors: | , , , , , , , , , , |
| Format: | Journal Article |
| Language: | English |
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13.09.2019
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| ISSN: | 1095-9203, 1095-9203 |
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| 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. |
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| AbstractList | 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-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-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. |
| Author | Iovan, Diana A Li, Alex Nordlund, Dennis Irwin, Kent D Lancaster, Kyle M DiMucci, Ida M Lee, Sang Jun Carsch, Kurtis M Zheng, Shao-Liang Titus, Charles J Betley, Theodore A |
| Author_xml | – sequence: 1 givenname: Kurtis M orcidid: 0000-0003-4432-7518 surname: Carsch fullname: Carsch, Kurtis M organization: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA – sequence: 2 givenname: Ida M orcidid: 0000-0003-3440-7856 surname: DiMucci fullname: DiMucci, Ida M organization: Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA – sequence: 3 givenname: Diana A orcidid: 0000-0001-9889-7183 surname: Iovan fullname: Iovan, Diana A organization: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA – sequence: 4 givenname: Alex orcidid: 0000-0001-9912-1643 surname: Li fullname: Li, Alex organization: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA – sequence: 5 givenname: Shao-Liang orcidid: 0000-0002-6432-9943 surname: Zheng fullname: Zheng, Shao-Liang organization: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA – sequence: 6 givenname: Charles J orcidid: 0000-0001-6312-8552 surname: Titus fullname: Titus, Charles J organization: Department of Physics, Stanford University, Stanford, CA, USA – sequence: 7 givenname: Sang Jun orcidid: 0000-0002-8199-3993 surname: Lee fullname: Lee, Sang Jun organization: Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USA – sequence: 8 givenname: Kent D orcidid: 0000-0002-2998-9743 surname: Irwin fullname: Irwin, Kent D organization: SLAC National Accelerator Laboratory, Menlo Park, CA, USA – sequence: 9 givenname: Dennis orcidid: 0000-0001-9524-6908 surname: Nordlund fullname: Nordlund, Dennis organization: Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USA – sequence: 10 givenname: Kyle M orcidid: 0000-0001-7296-128X surname: Lancaster fullname: Lancaster, Kyle M email: betley@chemistry.harvard.edu, kml236@cornell.edu organization: Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA. betley@chemistry.harvard.edu kml236@cornell.edu – sequence: 11 givenname: Theodore A orcidid: 0000-0001-5946-9629 surname: Betley fullname: Betley, Theodore A email: betley@chemistry.harvard.edu, kml236@cornell.edu organization: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA. betley@chemistry.harvard.edu kml236@cornell.edu |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/31515388$$D View this record in MEDLINE/PubMed |
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| Title | Synthesis of a copper-supported triplet nitrene complex pertinent to copper-catalyzed amination |
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