Synthesis, structure and spectroscopy of new thiopyrone and hydroxypyridinethione transition-metal complexes

The coordination chemistry of several O,S mixed donor ligands, namely thiopyrone and hydroxypyridinethione chelators, with a variety of middle and late first-row transition-metal ions is described. Complexes of 3-hydroxy-2-methyl-4-thiopyrone (thiomaltol) with cobalt(II), copper(II) and zinc(II); 3-...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2005-08 (15), p.2588-2596
Main Authors: Lewis, Jana A, Tran, Ba L, Puerta, David T, Rumberger, Evan M, Hendrickson, David N, Cohen, Seth M
Format: Article
Language:English
Subjects:
Cobalt - chemistry
Copper - chemistry
Crystallography, X-Ray
Electrochemistry
Iron - chemistry
Ligands
Magnetics
Models, Molecular
Molecular Structure
Nickel - chemistry
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
Pyridines - chemistry
Pyrones - chemistry
Sensitivity and Specificity
Spectrophotometry, Ultraviolet - methods
Thiones - chemistry
Transition Elements - chemistry
Zinc - chemistry
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Summary:The coordination chemistry of several O,S mixed donor ligands, namely thiopyrone and hydroxypyridinethione chelators, with a variety of middle and late first-row transition-metal ions is described. Complexes of 3-hydroxy-2-methyl-4-thiopyrone (thiomaltol) with cobalt(II), copper(II) and zinc(II); 3-hydroxy-1,2-dimethyl-4(1H)-pyridinethione (3,4-HOPTO) with iron(III), nickel(II), copper(II) and zinc(II); and 3-hydroxy-1-methyl-2(1H)-pyridinethione (3,2-HOPTO) with iron(III), nickel(II), copper(II) and zinc(II) have been synthesized and characterized. The structures, absorbance spectroscopy, cyclic voltammetry and superconducting quantum interferometer device (SQUID) measurements of selected metal complexes, as well as ligand protonation constants, are reported. Most of the metal complexes show coordination geometries indicative of a strong trans influence by the O,S chelators. The data presented herein provide the most detailed study of the transition-metal coordination chemistry of both thiopyrone and hydroxypyridinethione O,S donor ligands to date, and provide the basis for the investigation of these ligands in realm of biological inorganic chemistry.
ISSN:1477-9226
1477-9234
DOI:10.1039/b505034k