S-alkylation of soft scorpionates

Rajeev Rajasekharan Nair, Dean Moore, Kirsten Chalmers, Dawn Wallace, Louise M. Diamond, Lisa Darby, David Armstrong, John Reglinski, Mark Spicer

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9 Citations (Scopus)

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.
Original languageEnglish
Pages (from-to)2487-2495
Number of pages9
JournalChemistry - A European Journal
Volume19
Issue number7
Early online date7 Jan 2013
DOIs
Publication statusPublished - 11 Feb 2013

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Keywords

  • scorpionates
  • S-alkylation
  • alkylation

Cite this

Rajasekharan Nair, R., Moore, D., Chalmers, K., Wallace, D., Diamond, L. M., Darby, L., ... Spicer, M. (2013). S-alkylation of soft scorpionates. Chemistry - A European Journal , 19(7), 2487-2495. https://doi.org/10.1002/chem.201202314