The stability of mercaptobenzothiazole based soft scorpionate complexes

Rajeev Rajasekharan Nair, Dean Moore, Mark Spicer, John Reglinski, Alan Kennedy

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The chemistry of the hydrotris(mercaptobenzothiazolyl)borate anion (Tbz) with metal salts (HgI2, SbI3, BiI3, CoCl2) is reported in an attempt to probe the stability of the of Tbz ligand once coordinated to hard and soft metals. Complexes of Tbz with bismuth, containing the [Bi(Tbz)I3]− anion, are stable, but with the other metals this is not the case. Although simple complexes such as [Hg(Tbz)I] and [E(Tbz)I3]− (E = Sb, Bi) can be isolated from the reaction mixtures, subsequent reactions lead to ligand modification or decomposition. In the presence of mercury and antimony we observe the formation of a hitherto unseen cationic pentacyclic heterocycle. With cobalt we observe a small quantity of a product which suggests a more complete decomposition. A simple benzothiazole (bz) adduct [Co(bz)2Cl2] has been identified, in which the Tbz ligand has disintegrated and the parent heterocycle, mercaptobenzothiazole, has been desulfurized. A rationale for these observations is given.
LanguageEnglish
Pages10276–10282
Number of pages7
JournalInorganic Chemistry
Volume53
Issue number19
Early online date19 Sep 2014
DOIs
Publication statusPublished - Sep 2014

Fingerprint

Metals
Ligands
ligands
Anions
metals
anions
Decomposition
decomposition
Antimony
Borates
Bismuth
Cobalt
antimony
borates
Mercury
bismuth
adducts
cobalt
Salts
chemistry

Keywords

  • soft scorpionates
  • hydrotris(benzothiazolyl)borate
  • ring closure
  • main group chemistry

Cite this

Rajasekharan Nair, R., Moore, D., Spicer, M., Reglinski, J., & Kennedy, A. (2014). The stability of mercaptobenzothiazole based soft scorpionate complexes. Inorganic Chemistry, 53(19), 10276–10282. https://doi.org/10.1021/ic5013236
Rajasekharan Nair, Rajeev ; Moore, Dean ; Spicer, Mark ; Reglinski, John ; Kennedy, Alan. / The stability of mercaptobenzothiazole based soft scorpionate complexes. In: Inorganic Chemistry. 2014 ; Vol. 53, No. 19. pp. 10276–10282.
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Rajasekharan Nair, R, Moore, D, Spicer, M, Reglinski, J & Kennedy, A 2014, 'The stability of mercaptobenzothiazole based soft scorpionate complexes' Inorganic Chemistry, vol. 53, no. 19, pp. 10276–10282. https://doi.org/10.1021/ic5013236

The stability of mercaptobenzothiazole based soft scorpionate complexes. / Rajasekharan Nair, Rajeev; Moore, Dean; Spicer, Mark; Reglinski, John; Kennedy, Alan.

In: Inorganic Chemistry, Vol. 53, No. 19, 09.2014, p. 10276–10282.

Research output: Contribution to journalArticle

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AB - The chemistry of the hydrotris(mercaptobenzothiazolyl)borate anion (Tbz) with metal salts (HgI2, SbI3, BiI3, CoCl2) is reported in an attempt to probe the stability of the of Tbz ligand once coordinated to hard and soft metals. Complexes of Tbz with bismuth, containing the [Bi(Tbz)I3]− anion, are stable, but with the other metals this is not the case. Although simple complexes such as [Hg(Tbz)I] and [E(Tbz)I3]− (E = Sb, Bi) can be isolated from the reaction mixtures, subsequent reactions lead to ligand modification or decomposition. In the presence of mercury and antimony we observe the formation of a hitherto unseen cationic pentacyclic heterocycle. With cobalt we observe a small quantity of a product which suggests a more complete decomposition. A simple benzothiazole (bz) adduct [Co(bz)2Cl2] has been identified, in which the Tbz ligand has disintegrated and the parent heterocycle, mercaptobenzothiazole, has been desulfurized. A rationale for these observations is given.

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