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S-Alkylation of Soft Scorpionates

Authors

  • Rajeev Rajasekharan-Nair,

    1. WestCHEM, Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (UK)
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  • Dean Moore,

    1. WestCHEM, Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (UK)
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  • Dr. Kirsten Chalmers,

    1. WestCHEM, Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (UK)
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  • Dr. Dawn Wallace,

    1. WestCHEM, Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (UK)
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  • Louise M. Diamond,

    1. WestCHEM, Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (UK)
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  • Lisa Darby,

    1. WestCHEM, Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (UK)
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  • Dr. David R. Armstrong,

    1. WestCHEM, Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (UK)
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  • Dr. John Reglinski,

    Corresponding author
    1. WestCHEM, Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (UK)
    • WestCHEM, Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (UK)
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  • Dr. Mark D. Spicer

    Corresponding author
    1. WestCHEM, Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (UK)
    • WestCHEM, Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (UK)
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Abstract

The alkylation reactions of soft scorpionates are reported. The hydrotris(S-alkyl-methimazolyl)borate dications (alkyl=methyl, allyl, benzyl), which were prepared by the reaction of TmMe anion and primary alkyl halides, have been isolated and structurally characterised. The reaction is, however, not universally successful. DFT analysis of these alkylation reactions (C[DOUBLE BOND]S versus B[BOND]H alkylation) indicates that the observed outcome is driven by kinetic factors. Extending the study to incorporate alternative imine thiones (mercaptobenzothiazole, bz; thiazoline, tz) led to the structural characterisation of di[aquo-μ-aquohydrotris(mercaptobenzothiazolyl)boratosodium], which contains sodium atoms in the κ3-S,S,S coordination mode. Alkylation of Na[Tbz] and Na[tzTtz] leads to decomposition resulting in the formation of the simple S-alkylated heterocycles. The analysis of the species involved in these reactions shows an inherent weakness in the B[BOND]N bond in soft scorpionates, which has implications for their use in more advanced chemistry.

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