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S‐Alkylation of Soft Scorpionates
Author(s) -
RajasekharanNair Rajeev,
Moore Dean,
Chalmers Kirsten,
Wallace Dawn,
Diamond Louise M.,
Darby Lisa,
Armstrong David R.,
Reglinski John,
Spicer Mark D.
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201202314
Subject(s) - alkylation , chemistry , alkyl , halide , imine , medicinal chemistry , decomposition , organic chemistry , catalysis
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 Tm Me 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 κ 3 ‐ 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.