Group 13 and lanthanide complexes with mixed O,S anionic ligands derived from maltol

Article abstract of DOI:10.1021/ic048693y

Four mixed O,S binding ligand precursors derived from maltol (3-hydroxy-2-methyl-4-pyrone) have been chelated to gallium(III), indium(III); and lanthanide(III) ions to yield a series of metal complexes. The four ligand precursors include two pyranthiones, 3-hydroxy-2-methyl-4-pyranthione, commonly known as thiomaltol (Htma), and 2-ethyl-3-hydroxy-4-pyranthione, commonly known as ethylthiomaltol (Hetma), and two pyridinethiones, 3-hydroxy-2-methyl-4(H)- pyridinethione (Hmppt) and 3-hydroxy-1,2-dimethyl-4-pyridinethione (Hdppt). Dimeric forms of the pyridinethiones, Hmppt dimer and Hdppt dimer, were also isolated and characterized. Complete characterization of the monomeric organic compounds is reported including acidity constants and crystal structures of Htma, Hetma, and Hdppt dimer. Reacting the four monomeric ligand precursors with Ga³⁺ and In³⁺ ions yielded new tris(bidentate ligand) complexes. X-ray-quality crystals of the fac isomer of Ga(tma)₃ were also obtained. New complexes with a range of lanthanides (Ln³⁺) were also synthesized with the two pyranthiones, Htma and Hetma. The synthesis reactions yielded complexes of the type LnL₃·xH₂O and LnL₂(OH)·xH₂O, as indicated by elemental analysis and spectroscopic evidence such as mass spectral data and IR and NMR spectra.