Standard Article

Coordination Chemistry of o-Semiquinones

Metal Phenolates (2013)

  1. Cortlandt G. Pierpont,
  2. Joseph K. Kelly

Published Online: 17 JUN 2013

DOI: 10.1002/9780470682531.pat0615

Patai's Chemistry of Functional Groups

Patai's Chemistry of Functional Groups

How to Cite

Pierpont, C. G. and Kelly, J. K. 2013. Coordination Chemistry of o-Semiquinones. Patai's Chemistry of Functional Groups. .

Author Information

  1. University of Colorado, Department of Chemistry and Biochemistry, Boulder, Colorado, USA

Publication History

  1. Published Online: 17 JUN 2013

Chemistry Terms

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Abstract

o-Semiquinone (SQ) radicals are ideally suited to chelate with transition metal ions. Ligand paramagnetism results in spin-coupling interactions with paramagnetic metal ions, and complexes containing multiple SQ ligands have magnetic properties resulting from inter-ligand coupling. The unpaired SQ electron resides in a ligand-localized π orbital close in energy with the valence d orbitals of many transition metal ions. Electron transfer between ligand and metal may be observed under equilibrium conditions by monitoring the temperature-dependence of spectral and magnetic properties in a process known as valence tautomerism. The redox potentials of common SQ ligands overlap with the redox potentials of metal ions contributing to redox series that may involve reversible electron transfer steps at both the metal and SQ ligands. Multielectron redox reactions involving SQ ligands are useful in small molecule transformations that involve substrate oxidation or reduction over a narrow range in electrochemical potential. These properties are unique to complexes containing ligands capable of changing their charged state by either intramolecular electron transfer within the complex molecule or by an exchange of charge with an external redox component. Reactions and processes of this type will be the focus of this review on the coordination chemistry of o-semiquinonate ligands.

Keywords:

  • transition metal;
  • o-semiquinonate;
  • magnetism;
  • paramagnetic exchange;
  • redox reactions;
  • valence tautomerism;
  • redox isomerism;
  • electron transfer

Featured Compounds

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  1. 1 - 17
Compound 1
Molecular Weight:506.33
Molecular Formula:C28H22FeN2O4
InChIKey:YJHVMNOBVZKKFF-UHFFFAOYSA-L
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Compound 2
Molecular Weight:559.7287
Molecular Formula:C30H56MnN4O2
InChIKey:NROUQKQAEAHUPT-UHFFFAOYSA-L
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Compound 4
Molecular Weight:622.228
Molecular Formula:C34H56N2O4Zn
InChIKey:AIAFNSSFLLEEFJ-UHFFFAOYSA-N
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Compound 5
Molecular Weight:719.6156
Molecular Formula:C42H60NiO6
InChIKey:SDRAXHWJQKPUAJ-UHFFFAOYSA-N
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Compound 6
Molecular Weight:1008.322
Molecular Formula:C56H80Cu2O8
InChIKey:BFBZYNMSJUMXGM-UHFFFAOYSA-N
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Compound 7
Molecular Weight:655.7319
Molecular Formula:C38H48CoN2O4
InChIKey:VXLQJBMIKROTJR-UHFFFAOYSA-L
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Compound 8
Molecular Weight:655.7319
Molecular Formula:C38H48CoN2O4
InChIKey:SPJWNZZOKQNVCE-UHFFFAOYSA-N
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Compound 9
Molecular Weight:1395.0212
Molecular Formula:C86H146CoN2O8
InChIKey:JNLWIVLDGFVLDU-UHFFFAOYSA-L
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Compound 10
Molecular Weight:1395.0212
Molecular Formula:C86H146CoN2O8
InChIKey:RLBPQFKFCPGVKB-UHFFFAOYSA-N
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Compound 11
Molecular Weight:1391.0261
Molecular Formula:C86H146MnN2O8
InChIKey:ROVKKVLBMALEBD-UHFFFAOYSA-N
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Compound 12
Molecular Weight:1391.0261
Molecular Formula:C86H146MnN2O8
InChIKey:ORVOONPPMLUIMA-UHFFFAOYSA-L
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Compound 13
Molecular Weight:1391.0261
Molecular Formula:C86H146MnN2O8
InChIKey:NLALZSCVGZIYKA-UHFFFAOYSA-J
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Compound 14
Molecular Weight:1336.486
Molecular Formula:C78H84Cu2O4P4
InChIKey:BIGUTSDOKDLFLK-UHFFFAOYSA-N
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Compound 15
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 16
Molecular Weight:1383.458
Molecular Formula:C66H46Cl8FeO7P3
InChIKey:SWXORNCQBSBSMZ-UHFFFAOYSA-K
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Compound 17
Molecular Weight:2210.22
Molecular Formula:C112H160Mo4O20
InChIKey:RGXLKLUBQGYXBI-UHFFFAOYSA-A
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Compound 18
Molecular Weight:903.14
Molecular Formula:C50H38ClO4P2Rh
InChIKey:BRFYILXAYWMNLX-UHFFFAOYSA-L
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  1. 1 - 17