Xanthene-modified and hangman iron corroles.
Iron corroles modified with a xanthene scaffold are delivered from easily available starting materials in abbreviated reaction times. These new iron corroles have been spectroscopically examined with particular emphasis on defining the oxidation state of the metal center. Investigation of their electronic structure using (57)Fe Mössbauer spectroscopy in conjunction with density functional theory (DFT) calculations reveals the non-innocence of the corrole ligand. Although these iron corroles contain a formal Fe(IV) center, the deprotonated corrole macrocycle ligand is one electron oxidized. The electronic ground state of these complexes is best described as an intermediate spin S = 3/2 Fe(III) site strongly antiferromagnetically coupled to the S = 1/2 of the monoradical dianion corrole [Fe(III)Cl-corrole(+•)]. We show here that iron corroles as well as xanthene-modified and hangman xanthene iron corroles are redox active and catalyze the disproportionation of hydrogen peroxide via the catalase reaction, and that this activity scales with the oxidation potential. The meso position of corrole macrocycle is susceptible toward nucleophilic attack during catalase turnover. The reactivity of peroxide within the hangman cleft reported here adds to the emerging theme that corroles are good at catalyzing two-electron activation of the oxygen-oxygen bond in a variety of substrates.
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States. matthias.schwalbe@chemie.hu-berlin.de
Matthias
M
Schwalbe
Dilek K
DK
Dogutan
Sebastian A
SA
Stoian
Thomas S
TS
Teets
Daniel G
DG
Nocera
D002374:Catalase / Q000378:metabolism; D002384:Catalysis; D020134:Catalytic Domain; D002712:Chlorides / Q000737:chemistry; D004583:Electrons; D005290:Ferric Compounds / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry / Q000378:metabolism; D007501:Iron / Q000737:chemistry; D008024:Ligands; D008665:Metalloporphyrins / Q000737:chemistry* / Q000378:metabolism; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D011789:Quantum Theory; D015204:Spectroscopy, Mossbauer; D014867:Water / Q000737:chemistry; D014966:Xanthenes / Q000737:chemistry*
D002712:Chlorides; D005290:Ferric Compounds; D008024:Ligands; D008665:Metalloporphyrins; D014966:Xanthenes; C546809:iron corrole; D014867:Water; D006861:Hydrogen Peroxide; D007501:Iron; D002374:Catalase; D010100:Oxygen; C024555:ferric chloride