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Indenyl Rhodium Complexes with Arene Ligands: Synthesis and Application for Reductive Amination

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    Indenyl Rhodium Complexes with Arene Ligands: Synthesis and Application for Reductive Amination
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    • Vladimir B. Kharitonov
      Vladimir B. Kharitonov
      A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str. 28, 119991 Moscow, Russian Federation
      More by Vladimir B. Kharitonov
    • Maria Makarova
      Maria Makarova
      Dmitry Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, Moscow 125047, Russian Federation
      More by Maria Makarova
    • Mikhail A. Arsenov
      Mikhail A. Arsenov
      A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str. 28, 119991 Moscow, Russian Federation
      More by Mikhail A. Arsenov
    • Yulia V. Nelyubina
      Yulia V. Nelyubina
      A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str. 28, 119991 Moscow, Russian Federation
      More by Yulia V. Nelyubina
      Orcidhttp://orcid.org/0000-0002-9121-0040
    • Olga Chusova
      Olga Chusova
      Faculty of Science, RUDN University, 6 Miklukho-Maklaya St., Moscow 117198, Russian Federation
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    • Alexander S. Peregudov
      Alexander S. Peregudov
      A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str. 28, 119991 Moscow, Russian Federation
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    • Semen S. Zlotskii
      Semen S. Zlotskii
      Ufa Oil Institute, Kosmonavtov Str., 1, Ufa 450062, Russian Federation
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    • Denis Chusov
      Denis Chusov
      A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str. 28, 119991 Moscow, Russian Federation
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      Orcidhttp://orcid.org/0000-0001-6770-5484
    • Dmitry A. Loginov*
      Dmitry A. Loginov
      A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str. 28, 119991 Moscow, Russian Federation
      *E-mail for D.A.L.: [email protected]
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      Orcidhttp://orcid.org/0000-0002-7512-5057
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    Organometallics

    Cite this: Organometallics 2018, 37, 15, 2553–2562
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    https://doi.org/10.1021/acs.organomet.8b00311
    Published July 24, 2018
    Copyright © 2018 American Chemical Society
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    Abstract

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    An efficient protocol for synthesis of indenyl rhodium complexes with arene ligands has been developed. The hexafluoroantimonate salts [(η5-indenyl)Rh(arene)](SbF6)2 (arene = benzene (2a), o-xylene (2b), mesitylene (2c), durene (2d), hexamethylbenzene (2e), and [2.2]paracyclophane (2g)) were obtained by iodide abstraction from [(η5-indenyl)RhI2]n (1) with AgSbF6 in the presence of benzene and its derivatives. The procedure is also suitable for the synthesis of the dirhodium arene complex [(μ-η:η′-1,3-dimesitylpropane){Rh(η5-indenyl)}2](SbF6)4 (3) starting from 1,3-dimesitylpropane. The structures of [2e](SbF6)2, [2g](SbF6)2, and [3](SbF6)4 were determined by X-ray diffraction. The last species has a sterically unfavorable conformation, in which the bridgehead carbon atoms of the indenyl ligand are arranged close to the propane linker between two mesitylene moieties. Experimental and DFT calculation data revealed that the benzene ligand in 2a is more labile than that in the related cyclopentadienyl complexes [(C5R5)Rh(C6H6)]2+. Complex 2c effectively catalyzes the reductive amination reaction between aldehydes and primary (or secondary) amines in the presence of carbon monoxide, giving the corresponding secondary and tertiary amines in very high yields (80–99%). This protocol is the most active in water.

    Copyright © 2018 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.8b00311.

    • Crystallographic data and NMR spectra (PDF)

    • Cartesian coordinates for optimized structures (XYZ)

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    CCDC 1838580–1838582 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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    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

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    This article is cited by 27 publications.

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    3. Ping Li, Zexing Cao. Mechanism Insight into the Csp3–H Amination Catalyzed by the Metal Phthalocyanine. Organometallics 2019, 38 (2) , 343-350. https://doi.org/10.1021/acs.organomet.8b00747
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    Organometallics

    Cite this: Organometallics 2018, 37, 15, 2553–2562
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.organomet.8b00311
    Published July 24, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

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