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Thione-Thiol Tautomerism in Cobalt(II) Complexes

Thione-Thiol Tautomerism in Cobalt(II) Complexes. Objectives: --Synthesize Co complexes of an ambidentate ligand --Characterize with IR and electronic spectroscopy *Determine geometry and exact coordination sphere. MIMT: Ambidentate Tautomeric Ligand.

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Thione-Thiol Tautomerism in Cobalt(II) Complexes

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  1. Thione-Thiol Tautomerism in Cobalt(II) Complexes Objectives: --Synthesize Co complexes of an ambidentate ligand --Characterize with IR and electronic spectroscopy *Determine geometry and exact coordination sphere

  2. MIMT: Ambidentate Tautomeric Ligand 1,3-dihydro-1-methyl-2H-imidazole-2-thione 2-mercapto-1-methylimidazole

  3. Tautomerism --Tautomers: structural isomers --Interconversion always involves bond breaking and forming

  4. Ambidentate --Can bind to metal with different donor atoms M-S bond M-N bond

  5. Co Complexes of MIMT (A)[Co(MIMT)4(NO3)2] and (B)[Co(MIMT)2 (NO3)2] *Which tautomer is ligated? --all thione or all thiol, no mixed-ligand complexes --both thione complexes, both thiols, or one of each --complex obtained depends on: -quantity of MIMT added -solvent: can cause interconversion

  6. Co Complexes of MIMT (A)[Co(MIMT)4(NO3)2] and (B)[Co(MIMT)2 (NO3)2] *What is coordination sphere and geometry of A? (B): nitrates bound coordination sphere L2O2: Td However (A): nitrates bound or counterions? coordination sphere L4O2: Oh or coordination sphere L4: Td

  7. Characterization of Products DO DT Co2+ C S • UV-VIS spectroscopy • probes crystal field gap • IR spectroscopy • probes atomic motion

  8. IR Spectrum: Free MIMT

  9. Safety • Aqueous Co2+ complexes: liquid waste bottle. • Wear gloves when working with MIMT MIMT used when treating hyperthyroidism: at some dose dangerous Paracelsus, 16th century: “All substances are poisons. There is no substance that is not a poison. The only difference between a poison and a remedy is the dose.”

  10. Summary --Synthesize Co(II) complexes of an ambidentate, tautomeric, ligand *Use IR and electronic spectroscopy to determine geometries and exact coordination spheres*

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