Nitrogen Insertion into a Corrole Ring: Iridium Monoazaporphyrins

Authors

  • Dr. Joshua H. Palmer,

    Corresponding author
    1. Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., Pasadena, CA 91125 (USA)
    • Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., Pasadena, CA 91125 (USA)
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  • Theis Brock-Nannestad,

    1. Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., Pasadena, CA 91125 (USA)
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  • Dr. Atif Mahammed,

    1. Schulich Faculty of Chemistry, Technion—Israel Institute of Technology, Haifa 32000 (Israel)
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  • Alec C. Durrell,

    1. Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., Pasadena, CA 91125 (USA)
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  • Dr. David VanderVelde,

    1. Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., Pasadena, CA 91125 (USA)
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  • Dr. Scott Virgil,

    1. Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., Pasadena, CA 91125 (USA)
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  • Prof. Zeev Gross,

    1. Schulich Faculty of Chemistry, Technion—Israel Institute of Technology, Haifa 32000 (Israel)
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  • Prof. Harry B. Gray

    1. Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., Pasadena, CA 91125 (USA)
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  • This work was supported by the NSF (CCI Solar, CHE-0802907 and CHE-0947829), the US-Israel BSF, CCSER (Gordon and Betty Moore Foundation), and the Arnold and Mabel Beckman Foundation. We thank Drs. Lawrence M. Henling and Michael W. Day for assistance with the acquisition and analysis of crystallographic data.

Abstract

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A new route to rare porphyrinoids: The non-innocence of the corrole ring allows the oxidative ring insertion of a nitrogen atom under mild conditions (see scheme; NBS=N-bromosuccinimide). The resulting meso-substituted azaporphyrins exhibit high-energy Soret absorption bands and red luminescence. This new synthetic route will allow for the development of novel azaporphyrin complexes with relevance to the study of biomimetic oxidations.

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