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A Ruthenium Hydrido Dinitrogen Core Conserved across Multielectron/Multiproton Changes to the Pincer Ligand Backbone

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    A Ruthenium Hydrido Dinitrogen Core Conserved across Multielectron/Multiproton Changes to the Pincer Ligand Backbone
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    † Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, United States
    ‡ University of Goettingen, Institute for Inorganic Chemistry, 37077 Goettingen, Germany
    *E-mail: [email protected]
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2018, 57, 4, 1964–1975
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    https://doi.org/10.1021/acs.inorgchem.7b02889
    Published February 8, 2018
    Copyright © 2018 American Chemical Society
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    Abstract

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    A series of ruthenium(II) hydrido dinitrogen complexes supported by pincer ligands in different formal oxidation states have been prepared and characterized. Treating a ruthenium dichloride complex supported by the pincer ligand bis(di-tert-butylphosphinoethyl)amine (H-PNP) with reductant or base generates new five-coordinate cis-hydridodinitrogen ruthenium complexes each containing different forms of the pincer ligand. Further ligand transformations provide access to the first isostructural set of complexes featuring all six different forms of the pincer ligand. The conserved cis-hydridodinitrogen structure facilitates characterization of the π-donor, π-acceptor, and/or σ-donor properties of the ligands and assessment of the impact of ligand-centered multielectron/multiproton changes on N2 activation. Crystallographic studies, infrared spectroscopy, and 15N NMR spectroscopy indicate that N2 remains weakly activated in all cases, providing insight into the donor properties of the different pincer ligand states. Ramifications on applications of (pincer)Ru species in catalysis are considered.

    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.inorgchem.7b02889.

    • NMR and IR spectra of new complexes, electrochemistry data, and crystallographic details (PDF)

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    CCDC 1582272–1582278 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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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2018, 57, 4, 1964–1975
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.7b02889
    Published February 8, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

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