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1.
J Am Chem Soc ; 144(50): 22826-22830, 2022 12 21.
Article in English | MEDLINE | ID: mdl-36493464

ABSTRACT

A Co(II) complex with the polydentate quinol-containing ligand H2qp1 acts as an efficient electrocatalyst for oxygen reduction. Without any additional electron-proton transfer mediators, the electrocatalysis is selective for H2O; a related complex that substitutes a phenol for the quinol, conversely, instead produces mostly H2O2 under the same conditions. We propose that the ability of the redox-active quinol to donate two electrons impacts the product-determining step.


Subject(s)
Hydrogen Peroxide , Hydroquinones , Oxidation-Reduction , Electron Transport , Oxygen
2.
Chemistry ; 28(46): e202201179, 2022 Aug 16.
Article in English | MEDLINE | ID: mdl-35666136

ABSTRACT

A highly water- and air-stable Fe(II) complex with the quinol-containing macrocyclic ligand H4 qp4 reacts with H2 O2 to yield Fe(III) complexes with less highly chelating forms of the ligand that have either one or two para-quinones. The reaction increases the T1 -weighted relaxivity over four-fold, enabling the complex to detect H2 O2 using clinical MRI technology. The iron-containing sensor differs from its recently characterized manganese analog, which also detects H2 O2 , in that it is the oxidation of the metal center, rather than the ligand, that primarily enhances the relaxivity.


Subject(s)
Contrast Media , Iron , Ligands , Magnetic Resonance Imaging , Water
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