S-alkylation of soft scorpionates

Rajasekharan Nair, Rajeev and Moore, Dean and Chalmers, Kirsten and Wallace, Dawn and Diamond, Louise M. and Darby, Lisa and Armstrong, David and Reglinski, John and Spicer, Mark (2013) S-alkylation of soft scorpionates. Chemistry - A European Journal, 19 (7). pp. 2487-2495. ISSN 1521-3765 (https://doi.org/10.1002/chem.201202314)

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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 (CS versus BH 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 BN bond in soft scorpionates, which has implications for their use in more advanced chemistry.

ORCID iDs

Rajasekharan Nair, Rajeev, Moore, Dean, Chalmers, Kirsten, Wallace, Dawn, Diamond, Louise M., Darby, Lisa, Armstrong, David, Reglinski, John ORCID logoORCID: https://orcid.org/0000-0002-0263-4168 and Spicer, Mark ORCID logoORCID: https://orcid.org/0000-0002-6000-5677;
  • Item type:Article
    ID code:42905
    Dates:
    Date
    Event
    11 February 2013
    Published
    7 January 2013
    Published Online
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:18 Feb 2013 15:16
    Last modified:11 Nov 2024 10:20
    URI:https://strathprints.strath.ac.uk/id/eprint/42905
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