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Diverse Functionalization of Ruthenium-Chelated 2-Picolylamines: Oxygenation, Dehydrogenation, Cyclization, and N-Dealkylation
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    Diverse Functionalization of Ruthenium-Chelated 2-Picolylamines: Oxygenation, Dehydrogenation, Cyclization, and N-Dealkylation
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    • Sanjib Panda*
      Sanjib Panda
      Department of Chemistry, Indian Institute of Technology (IIT) Bombay, Powai, Mumbai 400076, India
      *Email: [email protected] (S.P.).
      More by Sanjib Panda
    • Arijit Singha Hazari
      Arijit Singha Hazari
      Department of Chemistry, Indian Institute of Technology (IIT) Bombay, Powai, Mumbai 400076, India
    • Manish Gogia
      Manish Gogia
      Department of Chemistry, Indian Institute of Technology (IIT) Bombay, Powai, Mumbai 400076, India
      More by Manish Gogia
    • Goutam Kumar Lahiri*
      Goutam Kumar Lahiri
      Department of Chemistry, Indian Institute of Technology (IIT) Bombay, Powai, Mumbai 400076, India
      *Email: [email protected] (G.K.L.).
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2020, 59, 2, 1355–1363
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    https://doi.org/10.1021/acs.inorgchem.9b03065
    Published January 7, 2020
    Copyright © 2020 American Chemical Society

    Abstract

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    “Chemical noninnocence” of metal-coordinated 2-picolylamine (PA) derivatives has been introduced upon its reaction with the metal precursor [RuII(Cl)(H)(CO)(PPh3)3] under basic conditions. This in effect leads to the facile formation of metalated amide, imine, ring-cyclized pyrrole, and an N-dealkylated congener based on the fine-tuning of an amine nitrogen (Namine) and a methylene center (Cα) at the PA backbone. It develops oxygenated L1′ in 1 and cyclized L4′ in 4 upon switching of the Namine substituent of PA from aryl to an electrophilic pent-3-en-2-one moiety. On the other hand, imposing the substituent at the Cα position of PA modifies its reactivity profile, leading to a dehydrogenation (2/3) or N-dealkylation (6) process. The divergent reactivity profile of metalated PA is considered to proceed through a common dianionic intermediate. Further, a competitive scenario of C–H bond functionalization of coordinated PA versus the ligand-exchange process has been exemplified in the presence of external electrophile such as benzyl bromide or methylene iodide. Authentication of the product formation as well as elucidation of the reaction pathway has been addressed by their crystal structures and spectroscopic features in conjunction with the transition-state (TS) theory.

    Copyright © 2020 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.9b03065.

    • MS spectra, crystal structures, NMR, GC–MS, crystallographic bond parameters, DFT-optimized structures, Gibbs free energy plot, and Cartesian coordinates (PDF)

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    CCDC 19512861951293 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    This article is cited by 18 publications.

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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2020, 59, 2, 1355–1363
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.9b03065
    Published January 7, 2020
    Copyright © 2020 American Chemical Society

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