title: An iron-peroxo porphyrin complex: new synthesis and reactivity toward a Cu(II) complex giving a heme-peroxo-copper adduct.
abstract: Side-on eta2-peroxo-iron porphyrins are strong nucleophiles. In cytochrome P450-like aromatase and other enzymes, such species are postulated as the active oxidants. In cytochrome c oxidase, hemea3-peroxo, hemea3-hydroperoxo, or hemea3-(mu-peroxo)-copper species are proposed as transient intermediates forming prior to O-O bond cleavage. In this report, we describe (1) a facile method for reduction of a heme-O2 species [(F8TPP)FeIII(O2-)(S)] (2), generating the ferric peroxo porphyrin complex [(F8TPP)FeIII(O22-)]- (3) (UV-vis, THF: lambdamax = 435 (Soret), 540(sh), 561; EPR: g = 8.7, 4.2), and (2) that this can be subsequently reacted with a ligand-copper(II) complex, [CuII(TMPA)-(CH3CN)](ClO4)2 (4), affording a heme-peroxo-copper heterobinuclear compound, [(F8TPP)FeII(O22-)-CuII(TMPA)](ClO4) (5). Generation of [(F8TPP)FeIII(O22-)]- (3) using cobaltocene as a one-electron reductant was monitored by UV-vis, EPR, and 1H NMR spectroscopies. Reaction between 3 and 4 was followed by UV-vis spectroscopy, and the product 5 could be precipitated and characterized. Coordination by copper(II) in 5 makes possible further reduction of the mu-peroxo complex by cobaltocene yielding the mu-oxo analogue, [(F8TPP)FeIII(O2-)-CuII(TMPA)](ClO4) (6).
authors.affiliation: Department of Chemistry, The Johns Hopkins University, Charles and 34th Streets, Baltimore, Maryland 21218, USA.
authors.forename: Eduardo E
authors.initials: EE
authors.lastname: Chufán
authors.forename: Kenneth D
authors.initials: KD
authors.lastname: Karlin
mesh_terms: D003300:Copper / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D006418:Heme / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D010084:Oxidation-Reduction; D013056:Spectrophotometry, Ultraviolet
chemical_list: D006418:Heme; D003300:Copper