S-alkylation of soft scorpionates

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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Citations (Scopus)


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-S versus B-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-N bond in soft scorpionates, which has implications for their use in more advanced chemistry. Alkylation reactions of soft scorpionates (see figure) are not universally successful. DFT analysis of these reactions indicates that the outcome is driven by kinetic factors. Di[aquo-μ- aquohydrotris(mercaptobenzothiazolyl)boratosodium] has been structurally characterized. The analysis of the species involved in these reactions shows that the B-N bond of soft scorpionates is weak.

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


  • B-N bonds
  • density functional calculations
  • ligands
  • S-alkylation
  • scorpionates

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry


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