title: Further insights into the spectroscopic properties, electronic structure, and kinetics of formation of the heme-peroxo-copper complex [(F8TPP)FeIII-(O2(2-)-CuII(TMPA)]+.
abstract: In the further development and understanding of heme-copper O2-reduction chemistry inspired by the active-site chemistry in cytochrome c oxidase, we describe a dioxygen adduct, [(F8TPP)FeIII-(O22-)-CuII(TMPA)](ClO4) (3), formed by addition of O2 to a 1:1 mixture of the porphyrinate-iron(II) complex (F8TPP)FeII (1a) {F8TPP = tetrakis(2,6-difluorophenyl)porphyrinate dianion} and the copper(I) complex [(TMPA)CuI(MeCN)](ClO4) (1b) {TMPA = tris(2-pyridylmethyl)amine}. Complex 3 forms in preference to heme-only or copper-only binuclear products, is remarkably stable {t1/2 (RT; MeCN) approximately 20 min; lambda max = 412 (Soret), 558 nm; EPR silent}, and is formulated as a peroxo complex on the basis of manometry {1a/1b/O2 = 1:1:1}, MALDI-TOF mass spectrometry {16O2, m/z 1239 [(3 + MeCN)+]; 18O2, m/z 1243}, and resonance Raman spectroscopy {nu(O-O) = 808 cm-1; Delta16O2/18O2 = 46 cm-1; Delta16O2/16/18O2 = 23 cm-1}. Consistent with a mu-eta2:eta1 bridging peroxide ligand, two metal-O stretching frequencies are observed {nu(Fe-O) = 533 cm-1, nu(Fe-O-Cu) = 511 cm-1}, and supporting normal coordinate analysis is presented. 2H and 19F NMR spectroscopies reveal that 3 is high-spin {also muB = 5.1 +/- 0.2, Evans method} with downfield-shifted pyrrole and upfield-shifted TMPA resonances, similar to the pattern observed for the structurally characterized mu-oxo complex [(F8TPP)FeIII-O-CuII(TMPA)]+ (4) (known S = 2 system, antiferromagnetically coupled high-spin FeIII and CuII). Mössbauer spectroscopy exhibits a sharp quadrupole doublet (zero field; delta = 0.57 mm/s, |DeltaEQ| = 1.14 mm/s) for 3, with isomer shift and magnetic field dependence data indicative of a peroxide ligand and S = 2 formulation. Both UV-visible-monitored stopped-flow kinetics and Mössbauer spectroscopic studies reveal the formation of heme-only superoxide complex (S)(F8TPP)FeIII-(O2-) (2a) (S = solvent molecule) prior to 3. Thermal decomposition of mu-peroxo complex 3 yields mu-oxo complex 4 with concomitant release of approximately 0.5 mol O2 per mol 3. Characterization of the reaction 1a/1b + O2 --> 2 --> 3 --> 4, presented here, advances our understanding and provides new insights to heme/Cu dioxygen-binding and reduction.
authors: Department of Chemistry, The Johns Hopkins University, Charles and 34th Streets, Baltimore, Maryland 21218, USA.
authors: Reza A
authors: RA
authors: Ghiladi
authors: Eduardo E
authors: EE
authors: Chufan
authors: Diego
authors: D
authors: del Río
authors: Edward I
authors: EI
authors: Solomon
authors: Carsten
authors: C
authors: Krebs
authors: Boi Hanh
authors: BH
authors: Huynh
authors: Hong-Wei
authors: HW
authors: Huang
authors: Pierre
authors: P
authors: Moënne-Loccoz
authors: Susan
authors: S
authors: Kaderli
authors: Marcus
authors: M
authors: Honecker
authors: Andreas D
authors: AD
authors: Zuberbühler
authors: Lisa
authors: L
authors: Marzilli
authors: Robert J
authors: RJ
authors: Cotter
authors: Kenneth D
authors: KD
authors: Karlin
mesh_terms: D003080:Cold Temperature; D003300:Copper / Q000737:chemistry*; D003903:Deuterium / Q000737:chemistry; D004563:Electrochemistry; D005462:Fluorine Radioisotopes / Q000737:chemistry; D006418:Heme / Q000737:chemistry*; D058085:Iron Compounds / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D010545:Peroxides / Q000737:chemistry; D012997:Solvents; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D015204:Spectroscopy, Mossbauer; D013059:Spectrum Analysis, Raman
chemical_list: D005462:Fluorine Radioisotopes; D058085:Iron Compounds; D009942:Organometallic Compounds; D010545:Peroxides; D012997:Solvents; D006418:Heme; D003300:Copper; D003903:Deuterium; D010100:Oxygen