Homo- and heteroleptic bismuth(III/V) thiolates from N-heterocyclic thiones: synthesis, structure and anti-microbial activity

Ahmad Luqman, Victoria L Blair, Rajini Brammananth, Paul K Crellin, Ross L Coppel, Philip C Andrews

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Abstract

Homo- and heteroleptic bismuth thiolato complexes have been synthesised and characterised from biolog,ically relevant tetrazole-, imidazole-, thiadiazole- and thia-zole- based heterocyclic thiones (thiols): 1-methyl-1 H-tetra-zole- 5-thiol (1-MMTZ(H)); 4-methyl-4 H-1,2,4-triazole-3-thiol (4-MTT(H)); 1-methyl-1 H-imidazole-2-thiol (2-MMI(H)); 5- methyl-1,3,4-thiadiazole-2-thiol (5-MMTD(H)); 1,3,4-thiadia-zole- 2-dithiol (2,5-DMTD(H)2); and 4-(4-bromophenyl)thia-zole- 2-thiol (4-BrMTD(H)). Reaction of BiPh3 with 1-MMTZ(H,) produced the rare BiV thiolato complex [BiPh(1-MMTZ,)4,/inf>], which undergoes reduction in DMSO to give [BiPh(1- MMTZ)2{(1-MMTZ(H)}2]. Reactions with PhBiCl2 or BiPh3 generally produced monophenylbismuth thiolates, [BiPh(SR)2]. The crystal structures of [BiPh(1-MMTZ)2{1-MMTZ(H)}2], [BiPh(5-MMTD)2], [BiPh{2,5-DMTD(H)}2(Me2C=O)] and [Bi(4- BrMTD)3] were obtained. Evaluation of the bactericidal properties against M. smegmatis, S. aureus, MRSA, VRE, E. faecalis and E. coli showed complexes containing the anionic ligands 1- MMTZ, 4-MTT and 4-BrMTD to be most effective. The dithiolato dithione complexes [BiPh(4-MTT)2{4-MTT(H)}2] and [BiPh(1-MMTZ)2{1-MMTZ(H)}2] were most effective against all the bacteria: MICs 0.34 m m for [BiPh(4-MTT)2 {4-MTT(H)}2] against VRE, and 1.33 mm for [BiPh(1-MMTZ)2{1-MMTZ(H)}2] against M. smegmatis and S. aureus. Tris-thiolato BiIII complexes were least effective overall. All complexes showed little or no toxicity towards mammalian COS-7 cells at 20 μgmL-1.

Original languageEnglish
Pages (from-to)14362-14377
Number of pages16
JournalChemistry - A European Journal
Volume20
Issue number44
DOIs
Publication statusPublished - 2014

Keywords

  • Bacteria
  • Bismuth
  • Structure elucidation
  • Synthesis,thiolate

Cite this

@article{370fa3da8d4e43e1ae5a35acabd5c908,
title = "Homo- and heteroleptic bismuth(III/V) thiolates from N-heterocyclic thiones: synthesis, structure and anti-microbial activity",
abstract = "Homo- and heteroleptic bismuth thiolato complexes have been synthesised and characterised from biolog,ically relevant tetrazole-, imidazole-, thiadiazole- and thia-zole- based heterocyclic thiones (thiols): 1-methyl-1 H-tetra-zole- 5-thiol (1-MMTZ(H)); 4-methyl-4 H-1,2,4-triazole-3-thiol (4-MTT(H)); 1-methyl-1 H-imidazole-2-thiol (2-MMI(H)); 5- methyl-1,3,4-thiadiazole-2-thiol (5-MMTD(H)); 1,3,4-thiadia-zole- 2-dithiol (2,5-DMTD(H)2); and 4-(4-bromophenyl)thia-zole- 2-thiol (4-BrMTD(H)). Reaction of BiPh3 with 1-MMTZ(H,) produced the rare BiV thiolato complex [BiPh(1-MMTZ,)4,/inf>], which undergoes reduction in DMSO to give [BiPh(1- MMTZ)2{(1-MMTZ(H)}2]. Reactions with PhBiCl2 or BiPh3 generally produced monophenylbismuth thiolates, [BiPh(SR)2]. The crystal structures of [BiPh(1-MMTZ)2{1-MMTZ(H)}2], [BiPh(5-MMTD)2], [BiPh{2,5-DMTD(H)}2(Me2C=O)] and [Bi(4- BrMTD)3] were obtained. Evaluation of the bactericidal properties against M. smegmatis, S. aureus, MRSA, VRE, E. faecalis and E. coli showed complexes containing the anionic ligands 1- MMTZ, 4-MTT and 4-BrMTD to be most effective. The dithiolato dithione complexes [BiPh(4-MTT)2{4-MTT(H)}2] and [BiPh(1-MMTZ)2{1-MMTZ(H)}2] were most effective against all the bacteria: MICs 0.34 m m for [BiPh(4-MTT)2 {4-MTT(H)}2] against VRE, and 1.33 mm for [BiPh(1-MMTZ)2{1-MMTZ(H)}2] against M. smegmatis and S. aureus. Tris-thiolato BiIII complexes were least effective overall. All complexes showed little or no toxicity towards mammalian COS-7 cells at 20 μgmL-1.",
keywords = "Bacteria, Bismuth, Structure elucidation, Synthesis,thiolate",
author = "Ahmad Luqman and Blair, {Victoria L} and Rajini Brammananth and Crellin, {Paul K} and Coppel, {Ross L} and Andrews, {Philip C}",
year = "2014",
doi = "10.1002/chem.201404109",
language = "English",
volume = "20",
pages = "14362--14377",
journal = "Chemistry - A European Journal",
issn = "1521-3765",
publisher = "Wiley-VCH Verlag GmbH & Co. KGaA",
number = "44",

}

Homo- and heteroleptic bismuth(III/V) thiolates from N-heterocyclic thiones: synthesis, structure and anti-microbial activity. / Luqman, Ahmad; Blair, Victoria L; Brammananth, Rajini; Crellin, Paul K; Coppel, Ross L; Andrews, Philip C.

In: Chemistry - A European Journal, Vol. 20, No. 44, 2014, p. 14362-14377.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Homo- and heteroleptic bismuth(III/V) thiolates from N-heterocyclic thiones: synthesis, structure and anti-microbial activity

AU - Luqman, Ahmad

AU - Blair, Victoria L

AU - Brammananth, Rajini

AU - Crellin, Paul K

AU - Coppel, Ross L

AU - Andrews, Philip C

PY - 2014

Y1 - 2014

N2 - Homo- and heteroleptic bismuth thiolato complexes have been synthesised and characterised from biolog,ically relevant tetrazole-, imidazole-, thiadiazole- and thia-zole- based heterocyclic thiones (thiols): 1-methyl-1 H-tetra-zole- 5-thiol (1-MMTZ(H)); 4-methyl-4 H-1,2,4-triazole-3-thiol (4-MTT(H)); 1-methyl-1 H-imidazole-2-thiol (2-MMI(H)); 5- methyl-1,3,4-thiadiazole-2-thiol (5-MMTD(H)); 1,3,4-thiadia-zole- 2-dithiol (2,5-DMTD(H)2); and 4-(4-bromophenyl)thia-zole- 2-thiol (4-BrMTD(H)). Reaction of BiPh3 with 1-MMTZ(H,) produced the rare BiV thiolato complex [BiPh(1-MMTZ,)4,/inf>], which undergoes reduction in DMSO to give [BiPh(1- MMTZ)2{(1-MMTZ(H)}2]. Reactions with PhBiCl2 or BiPh3 generally produced monophenylbismuth thiolates, [BiPh(SR)2]. The crystal structures of [BiPh(1-MMTZ)2{1-MMTZ(H)}2], [BiPh(5-MMTD)2], [BiPh{2,5-DMTD(H)}2(Me2C=O)] and [Bi(4- BrMTD)3] were obtained. Evaluation of the bactericidal properties against M. smegmatis, S. aureus, MRSA, VRE, E. faecalis and E. coli showed complexes containing the anionic ligands 1- MMTZ, 4-MTT and 4-BrMTD to be most effective. The dithiolato dithione complexes [BiPh(4-MTT)2{4-MTT(H)}2] and [BiPh(1-MMTZ)2{1-MMTZ(H)}2] were most effective against all the bacteria: MICs 0.34 m m for [BiPh(4-MTT)2 {4-MTT(H)}2] against VRE, and 1.33 mm for [BiPh(1-MMTZ)2{1-MMTZ(H)}2] against M. smegmatis and S. aureus. Tris-thiolato BiIII complexes were least effective overall. All complexes showed little or no toxicity towards mammalian COS-7 cells at 20 μgmL-1.

AB - Homo- and heteroleptic bismuth thiolato complexes have been synthesised and characterised from biolog,ically relevant tetrazole-, imidazole-, thiadiazole- and thia-zole- based heterocyclic thiones (thiols): 1-methyl-1 H-tetra-zole- 5-thiol (1-MMTZ(H)); 4-methyl-4 H-1,2,4-triazole-3-thiol (4-MTT(H)); 1-methyl-1 H-imidazole-2-thiol (2-MMI(H)); 5- methyl-1,3,4-thiadiazole-2-thiol (5-MMTD(H)); 1,3,4-thiadia-zole- 2-dithiol (2,5-DMTD(H)2); and 4-(4-bromophenyl)thia-zole- 2-thiol (4-BrMTD(H)). Reaction of BiPh3 with 1-MMTZ(H,) produced the rare BiV thiolato complex [BiPh(1-MMTZ,)4,/inf>], which undergoes reduction in DMSO to give [BiPh(1- MMTZ)2{(1-MMTZ(H)}2]. Reactions with PhBiCl2 or BiPh3 generally produced monophenylbismuth thiolates, [BiPh(SR)2]. The crystal structures of [BiPh(1-MMTZ)2{1-MMTZ(H)}2], [BiPh(5-MMTD)2], [BiPh{2,5-DMTD(H)}2(Me2C=O)] and [Bi(4- BrMTD)3] were obtained. Evaluation of the bactericidal properties against M. smegmatis, S. aureus, MRSA, VRE, E. faecalis and E. coli showed complexes containing the anionic ligands 1- MMTZ, 4-MTT and 4-BrMTD to be most effective. The dithiolato dithione complexes [BiPh(4-MTT)2{4-MTT(H)}2] and [BiPh(1-MMTZ)2{1-MMTZ(H)}2] were most effective against all the bacteria: MICs 0.34 m m for [BiPh(4-MTT)2 {4-MTT(H)}2] against VRE, and 1.33 mm for [BiPh(1-MMTZ)2{1-MMTZ(H)}2] against M. smegmatis and S. aureus. Tris-thiolato BiIII complexes were least effective overall. All complexes showed little or no toxicity towards mammalian COS-7 cells at 20 μgmL-1.

KW - Bacteria

KW - Bismuth

KW - Structure elucidation

KW - Synthesis,thiolate

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U2 - 10.1002/chem.201404109

DO - 10.1002/chem.201404109

M3 - Article

VL - 20

SP - 14362

EP - 14377

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 1521-3765

IS - 44

ER -