Role of proton-coupled electron transfer in O-O bond activation.

The selective reduction of oxygen to water requires four electrons and four protons. The design of catalysts that promote oxygen reduction therefore requires the management of both electron and proton inventories. Pacman and Hangman porphyrins provide a cleft for oxygen binding, a redox shuttle for oxygen reduction, and functionality for tuning the acid-base properties of bound oxygen and its intermediates. With proper control of the proton-coupled electron transfer events, O-O bond breaking of oxygen, and more generally oxygenated substrates, may be achieved with high efficiencies. The rule set developed for oxygen reduction may be applied to a variety of other small molecule activation reactions of consequence to energy conversion.

[1]  D. Nocera,et al.  Oxygen Activation Chemistry of Pacman and Hangman Porphyrin Architectures Based on Xanthene and Dibenzofuran Spacers , 2008 .

[2]  D. Nocera,et al.  Proton-directed redox control of O-O bond activation by heme hydroperoxidase models. , 2007, Journal of the American Chemical Society.

[3]  N. Devaraj,et al.  A Cytochrome c Oxidase Model Catalyzes Oxygen to Water Reduction Under Rate-Limiting Electron Flux , 2007, Science.

[4]  N. Lewis,et al.  Powering the planet: Chemical challenges in solar energy utilization , 2006, Proceedings of the National Academy of Sciences.

[5]  D. Nocera,et al.  Hangman salen platforms containing two xanthene scaffolds. , 2006, The Journal of organic chemistry.

[6]  D. Nocera.  On the future of global energy , 2006, Daedalus.

[7]  D. Nocera,et al.  Proton-coupled electron transfer: the mechanistic underpinning for radical transport and catalysis in biology , 2006, Philosophical Transactions of the Royal Society B: Biological Sciences.

[8]  Shih‐Yuan Liu,et al.  Mechanistic studies of Hangman salophen-mediated activation of O-O bonds. , 2006, Inorganic chemistry.

[9]  S. Ferguson-Miller,et al.  Energy transduction: proton transfer through the respiratory complexes. , 2006, Annual review of biochemistry.

[10]  D. Nocera,et al.  Photocatalytic oxidation of hydrocarbons by a bis-iron(III)-mu-oxo Pacman porphyrin using O2 and visible light. , 2006, Journal of the American Chemical Society.

[11]  R. Gennis,et al.  Controlled uncoupling and recoupling of proton pumping in cytochrome c oxidase. , 2006, Proceedings of the National Academy of Sciences of the United States of America.

[12]  Daniel G Nocera,et al.  Molecular chemistry of consequence to renewable energy. , 2005, Inorganic chemistry.

[13]  K. Kadish,et al.  Electrochemistry, spectroelectrochemistry, chloride binding, and O2 catalytic reactions of free-base porphyrin-cobalt corrole dyads. , 2005, Inorganic chemistry.

[14]  K. Kadish,et al.  Heterobimetallic complexes of cobalt(IV) porphyrin-corrole dyads. Synthesis, physicochemical properties, and X-ray structural characterization. , 2005, Inorganic chemistry.

[15]  K. Kadish,et al.  Cobalt(III) corroles as electrocatalysts for the reduction of dioxygen: reactivity of a monocorrole, biscorroles, and porphyrin-corrole dyads. , 2005, Journal of the American Chemical Society.

[16]  D. Nocera,et al.  Aerobic catalytic photooxidation of olefins by an electron-deficient Pacman bisiron(III) mu-oxo porphyrin. , 2005, The Journal of organic chemistry.

[17]  S. Adler.  Factors governing oxygen reduction in solid oxide fuel cell cathodes. , 2004, Chemical reviews.

[18]  M. Winter,et al.  What are batteries, fuel cells, and supercapacitors? , 2004, Chemical reviews.

[19]  S. Fukuzumi,et al.  Mechanism of four-electron reduction of dioxygen to water by ferrocene derivatives in the presence of perchloric acid in benzonitrile, catalyzed by cofacial dicobalt porphyrins. , 2004, Journal of the American Chemical Society.

[20]  Christopher J. Chang,et al.  Targeted proton delivery in the catalyzed reduction of oxygen to water by bimetallic pacman porphyrins. , 2004, Journal of the American Chemical Society.

[21]  M. Wikström.  Cytochrome c oxidase: 25 years of the elusive proton pump. , 2004, Biochimica et biophysica acta.

[22]  C. Sunderland,et al.  Functional analogues of cytochrome c oxidase, myoglobin, and hemoglobin. , 2004, Chemical reviews.

[23]  D. Nocera,et al.  Transient absorption studies of the Pacman effect in spring-loaded diiron(III) mu-oxo bisporphyrins. , 2003, Inorganic chemistry.

[24]  D. Nocera,et al.  The Pacman effect: a supramolecular strategy for controlling the excited-state dynamics of pillared cofacial bisporphyrins. , 2003, Inorganic chemistry.

[25]  C. Sunderland,et al.  Functional Analogues of the Dioxygen Reduction Site in Cytochrome Oxidase: Mechanistic Aspects and Possible Effects of CuB [J. Am. Chem. Soc. 2002, 124, 11923−11935]. , 2003 .

[26]  D. Nocera,et al.  Catalytic O[bond]O activation chemistry mediated by iron hangman porphyrins with a wide range of proton-donating abilities. , 2003, Organic letters.

[27]  Bernhard Kadenbach,et al.  Intrinsic and extrinsic uncoupling of oxidative phosphorylation. , 2003, Biochimica et biophysica acta.

[28]  D. Nocera,et al.  Meso-tetraaryl cofacial bisporphyrins delivered by Suzuki cross-coupling. , 2003, The Journal of organic chemistry.

[29]  D. Nocera,et al.  Proton-coupled O-O activation on a redox platform bearing a hydrogen-bonding scaffold. , 2003, Journal of the American Chemical Society.

[30]  D. Nocera,et al.  Excited-state dynamics of cofacial pacman porphyrins , 2002 .

[31]  F. Bolze,et al.  Alkyl and aryl substituted corroles. 3. Reactions of cofacial cobalt biscorroles and porphyrin-corroles with pyridine and carbon monoxide. , 2002, Inorganic chemistry.

[32]  D. Nocera,et al.  A phototriggered molecular spring for aerobic catalytic oxidation reactions. , 2002, Journal of the American Chemical Society.

[33]  D. Nocera,et al.  Structural, spectroscopic, and reactivity comparison of xanthene- and dibenzofuran-bridged cofacial bisporphyrins. , 2002, Inorganic chemistry.

[34]  D. Nocera,et al.  A convergent synthetic approach using sterically demanding aryldipyrrylmethanes for tuning the pocket sizes of cofacial bisporphyrins. , 2002, Inorganic chemistry.

[35]  D. Nocera,et al.  Porphyrin architectures bearing functionalized xanthene spacers. , 2002, The Journal of organic chemistry.

[36]  S. Ozaki,et al.  Investigations of the Roles of the Distal Heme Environment and the Proximal Heme Iron Ligand in Peroxide Activation by Heme Enzymes via Molecular Engineering of Myoglobin , 2001 .

[37]  M. Machius,et al.  Pivotal role of water in the mechanism of P450BM-3. , 2001, Biochemistry.

[38]  M. Wikström,et al.  Role of the PR intermediate in the reaction of cytochrome c oxidase with O2. , 2001, Biochemistry.

[39]  D. Nocera,et al.  "Hangman" porphyrins for the assembly of a model heme water channel. , 2001, Journal of the American Chemical Society.

[40]  M. Wikström,et al.  Modeling Cytochrome Oxidase: A Quantum Chemical Study of the O−O Bond Cleavage Mechanism , 2000 .

[41]  D. Nocera,et al.  Xanthene-bridged cofacial bisporphyrins. , 2000, Inorganic chemistry.

[42]  G. Babcock,et al.  From water to oxygen and back again: mechanistic similarities in the enzymatic redox conversions between water and dioxygen. , 1998, Biochimica et biophysica acta.

[43]  J. Saillard,et al.  Reactivity toward Dioxygen of Dicobalt Face-to-Face Diporphyrins in Aprotic Media. Experimental and Theoretical Aspects. Possible Mechanistic Implication in the Reduction of Dioxygen , 1997 .

[44]  C. Knobler,et al.  Host-guest complexation. 65. Six new saddle shaped hosts based on fused dibenzofuran units , 1992 .

[45]  F. Anson,et al.  Multiple intramolecular electron transfer in the catalysis of the reduction of dioxygen by cobalt meso-tetrakis(4-pyridyl)porphyrin to which four Ru(NH3)5 groups are coordinated , 1991 .

[46]  J. Nowick,et al.  Convergent functional groups. 9. Complexation in new molecular clefts , 1990 .

[47]  H. Taube.  Interaction of Dioxygen Species and Metal Ions. Equilibrium Aspects , 1987 .

[48]  A. Tulinsky,et al.  Crystal and molecular structure of anthracene and biphenylene pillared cofacial diporphyrins. , 1986, Journal of the American Chemical Society.

[49]  A. Bard,et al.  Standard Potentials in Aqueous Solution , 1985 .

[50]  Hsue-Yang Liu,et al.  Catalysis of the electroreduction of dioxygen and hydrogen peroxide by an anthracene-linked dimeric cobalt porphyrin , 1985 .

[51]  R. Young,et al.  SYNTHESIS AND CHARACTERIZATION OF BLOCKED AND LIGAND-APPENDED HEMES DERIVED FROM ATROPISOMERIC MESO-DIPHENYLPORPHYRINS , 1985 .

[52]  I. Abdalmuhdi,et al.  Electroreduction of oxygen by pillared cobalt(II) cofacial diporphyrin catalysts , 1984 .

[53]  R. Haushalter,et al.  High-valent iron-porphyrin complexes related to peroxidase and cytochrome P-450 , 1981 .

[54]  Shih‐Yuan Liu,et al.  Hangman salophens. , 2005, Journal of the American Chemical Society.

[55]  Roger Guilard,et al.  The porphyrin handbook , 2002 .

[56]  S. Chan,et al.  Structures and proton-pumping strategies of mitochondrial respiratory enzymes. , 2001, Annual review of biophysics and biomolecular structure.

[57]  D. Nocera,et al.  Electrocatalytic four-electron reduction of oxygen to water by a highly flexible cofacial cobalt bisporphyrin , 2000 .

[58]  D. Nocera,et al.  Direct Observation of the “Pac-Man” Effect from Dibenzofuran-Bridged Cofacial Bisporphyrins , 2000 .

[59]  B. Andrioletti,et al.  Electrocatalytic reduction of dioxygen to water by tren-capped porphyrins, functional models of cytochrome c oxidase† , 1999 .

[60]  Harry Julius Emeléus,et al.  Advances in Inorganic Chemistry and Radiochemistry , 1982 .

[61]  R. Mair,et al.  Determination of Organic Peroxides by Iodine Liberation Procedures. , 1964 .