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-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.
Lewis
Jana A
JA
Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California, USA.
Tran
Ba L
BL
Puerta
David T
DT
Rumberger
Evan M
EM
Hendrickson
David N
DN
Cohen
Seth M
SM
D003035:Cobalt / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D018360:Crystallography, X-Ray; D004563:Electrochemistry; D007501:Iron / Q000737:chemistry; D008024:Ligands; D008280:Magnetics; D008958:Models, Molecular; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D011753:Pyrones / Q000737:chemistry*; D012680:Sensitivity and Specificity; D013056:Spectrophotometry, Ultraviolet / Q000379:methods; D013871:Thiones / Q000737:chemistry*; D028561:Transition Elements / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry
D008024:Ligands; D009942:Organometallic Compounds; D011725:Pyridines; D011753:Pyrones; D013871:Thiones; D028561:Transition Elements; D003035:Cobalt; D003300:Copper; D009532:Nickel; D007501:Iron; D015032:Zinc