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New Selective Synthesis of Dithiaboroles as a Viable Pathway to Functionalized Benzenedithiolenes and Their Complexes

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    New Selective Synthesis of Dithiaboroles as a Viable Pathway to Functionalized Benzenedithiolenes and Their Complexes
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    † †Institute of Inorganic Chemistry, ‡Institute of Physical Chemistry, and §Institute of Organic Chemistry, University of Stuttgart, 70550 Stuttgart, Germany
    ∥ Laboratoire National des Champs Magnétiques Intenses, 38042 Grenoble, France
    *E-mail: [email protected]
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2016, 55, 12, 6186–6194
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    https://doi.org/10.1021/acs.inorgchem.6b00821
    Published June 1, 2016
    Copyright © 2016 American Chemical Society
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    Abstract

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    A synthetic protocol to synthesize 2-bromobenzo-1,3,2-dithiaboroles in one step from easily accessible benzene bis(isopropyl thioether)s has been developed. The reaction is remarkably specific in converting substrates with two adjacent iPrS moieties while leaving isolated thioether functions and other functional groups intact. On the basis of the spectroscopic detection or isolation of reaction intermediates, a mechanistic explanation involving a neighbor-group-assisted dealkylation as a key step is proposed. The resulting products featuring one or two dithiaborole units were isolated in good yields and fully characterized. Subsequent methanolysis, which was carried out either as a separate reaction step or in the manner of a one-pot reaction, gave rise to functionally substituted benzenedithiols. The feasibility of a methylphosphoryl-substituted benzenedithiol to act as a dianionic S,S-chelating ligand was demonstrated with the formation of paramagnetic Ni(III) and Co(III) complexes. Selective reduction of the phosphoryl group afforded a rare example of a phosphino dithiol which was shown to act as a monoanionic P,S-bidentate ligand toward Pd(II). All complexes were characterized by spectral data and X-ray diffraction studies, and the paramagnetic ones also by superconducting quantum interference device magnetometry.

    Copyright © 2016 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.6b00821.

    • Depiction of intermolecular interactions in crystalline dithioboroles, 1H and 11B NMR spectra of the thioether deprotection reactions, variable-temperature 1H and 31P NMR spectra of [NEt4]10, UV–vis spectra of [NEt4]10 and [NEt3H]11, magnetic measurements of [NEt4]10, EPR spectra of [NEt3H]11, and far-infrared spectra of [NEt4]10 (PDF)

    • Full crystallographic data for 1, 2, 4, 5, 7b, 7c, 7d′, 9d, and 10–12 as CIFs (ZIP)

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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2016, 55, 12, 6186–6194
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.6b00821
    Published June 1, 2016
    Copyright © 2016 American Chemical Society
    Request reuse permissions

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