Synthetic and structural comparisons of bismuth(iii) carboxylates synthesised under solvent-free and reflux conditions

Philip Craig Andrews, Glen Berenger Deacon, Peter Courtney Junk, Ish Kumar, Morry Silberstein

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Two synthetic approaches to the formation of bismuth(iii) carboxylates have been explored and compared. Ph3Bi was reacted with a series of carboxylic acids (RCO2H) of varying pK aand functionality (R = PhCH$#x2550;CH, o-MeOC6H4, m-MeOC6H4, o-H2NC6Ho-O2NC6H4, p-O2NC6H4, 2-(C5H4N)) under reflux conditions in toluene and solvent-free. The thermochemical profiles of the solvent-free reactions were also studied by DSC-TGA. All reactions produced the tri-substituted bismuth carboxylates in comparable yields and purity with the exceptions of picolinic acid and p-nitrobenzoic acid. 2-Picolinic acid exclusively formed the di-substituted complex, [PhBi(2-(C5H4N)CO2)2]4, by both methods, while p-nitrobenzoic acid gave the tri-substituted complex through reflux and the di-substituted complex under solvent-free conditions. Two of the complexes were structurally authenticated by single crystal X-ray diffraction: [PhBi(2-(C5H4N)CO2)2]4is tetrameric formed through five membered chelate rings involving the pyridyl N and O(-C) rather than the less stable carboxylate (-CO2) chelates, while [Bi(o-MeOC6H4CO2)3], is a polymer in which dimeric units, constructed around two chelating and one unsymmetrical bridging carboxylate on each Bi centre, are then joined together through longer intermolecular Bi–O bridging bonds.

Original languageEnglish
Pages (from-to)4852-4858
Number of pages7
JournalDalton Transactions
Issue number40
Publication statusPublished - 10 Oct 2006

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