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
UR - http://www.scopus.com/inward/record.url?scp=84915822264&partnerID=8YFLogxK
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 -