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Ferric Heme Superoxide Reductive Transformations to Ferric Heme (Hydro)Peroxide Species: Spectroscopic Characterization and Thermodynamic Implications for H-Atom Transfer (HAT).
Kim, Hyun; Rogler, Patrick J; Sharma, Savita K; Schaefer, Andrew W; Solomon, Edward I; Karlin, Kenneth D.
Afiliación
  • Kim H; Chemistry Department, Johns Hopkins University, Baltimore, MD, 21218, USA.
  • Rogler PJ; Chemistry Department, Johns Hopkins University, Baltimore, MD, 21218, USA.
  • Sharma SK; Chemistry Department, Johns Hopkins University, Baltimore, MD, 21218, USA.
  • Schaefer AW; Chemistry Department, Stanford University, Stanford, CA, 94305, USA.
  • Solomon EI; Chemistry Department, Stanford University, Stanford, CA, 94305, USA.
  • Karlin KD; Chemistry Department, Johns Hopkins University, Baltimore, MD, 21218, USA.
Angew Chem Int Ed Engl ; 60(11): 5907-5912, 2021 03 08.
Article en En | MEDLINE | ID: mdl-33348450
A new end-on low-spin ferric heme peroxide, [(PIm )FeIII -(O22- )]- (PIm -P), and subsequently formed hydroperoxide species, [(PIm )FeIII -(OOH)] (PIm -HP) are generated utilizing the iron-porphyrinate PIm with its tethered axial base imidazolyl group. Measured thermodynamic parameters, the ferric heme superoxide [(PIm )FeIII -(O2⋅- )] (PIm -S) reduction potential (E°') and the PIm -HP pKa value, lead to the finding of the OO-H bond-dissociation free energy (BDFE) of PIm -HP as 69.5 kcal mol-1 using a thermodynamic square scheme and Bordwell relationship. The results are validated by the observed oxidizing ability of PIm -S via hydrogen-atom transfer (HAT) compared to that of the F8 superoxide complex, [(F8 )FeIII -(O2.- )] (S) (F8 =tetrakis(2,6-difluorophenyl)porphyrinate, without an internally appended axial base imidazolyl), as determined from reactivity comparison of superoxide complexes PIm -S and S with the hydroxylamine (O-H) substrates TEMPO-H and ABNO-H.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Peróxidos / Termodinámica / Compuestos Férricos / Superóxidos / Hemo Idioma: En Revista: Angew Chem Int Ed Engl Año: 2021 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Alemania
Texto completo
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Peróxidos / Termodinámica / Compuestos Férricos / Superóxidos / Hemo Idioma: En Revista: Angew Chem Int Ed Engl Año: 2021 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Alemania