The decomposition of water to oxygen/hydrogen by the renewable energy and its inverse reaction, oxygen reduction to water, are fundamental ones in

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1 / The decomposition of water to oxygen/hydrogen by the renewable energy and its inverse reaction, oxygen reduction to water, are fundamental ones in hydrogen economy. Creation of catalysts to perform both four-electron reactions in high energy-efficiency is important for realizing it. However, since the existing catalysts are still immature and less efficient, we have studied to obtain deep understanding on these reactions modeling of metalloenzymes, which work in photosynthesis and respiration. According to this research, we succeeded to elucidate both reactions mechanism with elaborate (functional) models of the enzymes and to propose them as the excellent molecule catalysts.

2 (1) II (2) (3) (4) (1) c ; CcO - CCD ESR (2) CytP450, NO CcO (III)( ) (3) (i) - Cu II -O-O-Fe III Fe III -O-O (Cu I ) Tyr (ii) Cu I, Tyr-His Tyr Tyr CcO (CuB)-

3 CuB heme a3 Tyr heme a3 CuB Tyr (iii) Fe(III)=O (Compound II) Cu(II) (iv) N3 N4 µ η 2 :η 2, µ η 2 :η 1 (2) ( ) Fe(III)( ) end-on compound 0 side-on CcO (FeTMPIm ) (i) (PCET) PCET (ii) (O2 ) Fe(II) end-on (-75 ) Fe II TMPIm O2 end-on (iii) (O2 ) Fe(II) side-on end-on 1978 J. S. Valentine O2 (II) Fe II TMPIm side-on Fe(III) side-on end-on O2 (II) O2 7 side-on Fe(III) end-on

4 side-on ( 3) end-on (v), Formation of an End-On Ferric-Peroxo Intermediate upon One-ElectronReduction of a Ferric-Superoxo Heme. J.-G. Liu, Y. Shimizu, T. Ohta, and Y. Naruta, J. Am. Chem. Soc. 2010, 132, Copper(II) and Nickel(II) hexafluorophosphate complexes Derived from a Monoanionic Porphyrin Analogue: solvato- and Thermchromism of the Ni complexes by Spin-Interconversion, M. Ishida, Y. Naruta, and F. Tani, Dalton Trans., Issue cover & hot paper 2010, 39, A Novel Porphyrin-related Macrocycle with an Embedded 1,10-phenanthroline moiety as a fluorescent Mg(II) Ion Sensor, M. Ishida, Y. Naruta, and F. Tani, Angew. Chem. Int. Ed. 2010, 49, Using Synthetic Models to Probe the O 2 Metabolic Mechanism in Heme-Containing Enzymes, J.-G. Liu, T. Ohta, F. Tani, Y. Naruta, Science of Future Molecular Systems 2009, 3, Characterization of a Hydroperoxo-Heme Intermediate of a Synthetic Model: Conversion of a Side-on Peroxy to an End-on Hydroperoxy Complex, J.-G. Liu, T. Ohta, S. Yamaguchi, T. Ogura, S. Sakamoto, Y. Maeda, and Y. Naruta, Angew. Chem. Int. Ed., VIP 2009, 48, Synthesis and Characterization of a New Prostaglandin H Synthase Model, J. J. Reddy, T. Ohta, Y. Naruta, Tetrahedron Lett. (, 50 th Anniversary Issue, Invited paper) 2009, 50, Kinetic Investigation of the Process of Encapsulation of Small Hydrocarbon into a Cavitand Porphyrin. J. Nakazawa, Y. Sakae, M. Aida, and Y. Naruta, J. Org.

5 Chem. 2007, 72, Synthetic Models of the Active Site of Cytochrome c Oxidase: Influence of a Tridentate vs Tetradentate Copper Chelate Bearing a His-Tyr linkage Mimic on the Dioxygen Adduct Formation by Heme/Cu Complexes, J.-G. Liu, Y. Naruta, and F. Tani, Chem. Eur. J. 2007, 13, Characterization of Phenoxyl Radical in Model Complexes for the Cu B site of Cytochrome c Oxidase: Steady-State and Transient Absorption, UV resonance Raman, EPR, and DFT Studies for [M II BIAIPBr]Br, Y. Nagano, J.-G. Liu, Y. Naruta, T. Ikoma, S. Tero-Kubota and T. Kitagawa, J. Am. Chem. Soc. 2006, 128(45), , 58, , No. 424, pp Syntheses, Crystal Structures, and Single Small Molecule Encapsulation Properties of Cavitand-Porphyrins, J. Nakazawa, M. Mizuki, J. Hagiwara, Y. Shimazaki, F. Tani, Y. Naruta, Bull. Chem. Soc. Jpn, 2006, 79, Size-selective and Reversible Encapsulation of Single Small Hydrocarbon Molecules by a Cavitand-Porphyrin Species, J. Nakazawa, J. Hagiwara, M. Mizuki, Y. Shimazaki, F. Tani, and Y. Naruta, Angew. Chem. Int. Ed. ( 2005, 44, An Elaborate Functional Model of Cytochrome c Oxidase Active Site Displaying a Unique Conversion of a Heme-µ-peroxo-Cu II Species to a Heme-superoxo/Cu I, J.-G. Liu, Y. Naruta, and F. Tani, Angew. Chem. Int. Ed , (2005). UV Resonance Raman Study of Model Complexes of the Cu B Site of Cytochrome c Oxidase, Y. Nagano, J.-G. Liu, Y. Naruta, T. Kitagawa, J. Mol. Struct. 2005, , Selective Formation of a Stable µ-peroxo Ferric Heme-Cu II Complex from the Corresponding µ-oxo Fe III -Cu II Species and Hydrogen Peroxide, T. Chishiro, Y. Shimazaki, F. Tani, and Y. Naruta, Chem Commun (8), ( ) Synthetic Heme Models Mimic the Formation of Peroxo- and Hydroperoxo-heme Intermediates Relevant to Dioxygen Activation in Heme-containing Enzymes, J.-G. Liu, Asian International Conference in Coordination, Organometallic, and Inorganic Chemistry in 90th Annual Spring Meeting of CSJ, Funabashi, 28/3/2010. Peroxy to tan end-on Hydroperoxy, J.-G. Liu, T. Ohta, Y. Naruta, Recent progress in Porphyrin-related Chemistry (40th international Workshop on Future Molecular Systems 2010), Fukuoka, Japan, 1/2/2010. Dioxygen Activation on Chemical Models of Heme Enzymes, Y. Naruta, 12th international Symposium on Physical Organic Chemistry (KISPOC-12), Kyushu University, Fukuoka, Japan, 16/12/2009. Dioxygen Activation on Chemical Models of Heme Enzymes, Symposium of Advancement on Biological Inorganic Chemsitry (SaBIC), Y. Naruta, Tata Institute of Fundamental Research, Mumbai, India, 4/11/2009. Preparation of End-on Peroxy and Hydroperoxy Intermediates Relevant to Dioxygen Activation in Heme Enzymes and Cytochrome c Oxidase, Y. Naruta, International Workshop on Metalloprotein Functions, University of Hyogo, Harima, Japan, 31/7/2009. Simulation of O 2 Activation/Reduction with Enzyme Active Site Models of Terminal Oxidases, Y. Naruta, J.-G. Liu, T. Ohta, H. Ogura, 14th International Conference on Biological Inorganic Chemistry (ICBIC-14), Nagoya, Japan, 26/7/2009., 18-19/7/2008 Selective Preparation of End-on Ferric-Peroxo, Ferrous-Superoxo, and Ferric-Hydroperoxo Species in Solution, Y. Naruta International Union of Material Research Society-International Conference in Asia, Nagoya, 12/12/2008. Selective Preparation of End-on Metal Peroxy Complexes in a Solution and Their Relevance to Dioxygen Activation, Y. Naruta, J.-G. Liu, T. Ota, S. Yamaguchi, T. Ogura, 4th Asian Bioinorganic Chemistry

6 Conference (AsBIC IV), Jeju, Korea, 10-13/11/2008,, 89 -,, 27-30/3/2008. Mutual Conversion Reactions between Water and Oxygen with Metal Complexes, Y. Naruta, 57th Coordination Chemistry Symposium, Nagoya, 25/9/2007. Oxygen Activation and Oxygen Reduction with Bio-inspired Chemical Models, Y. Naruta. 3 rd Joint Symposium of Core Research Institutes, Multidisciplinary Approach for Materials Synthesis, Fukuoka, 15/3/2008. Manganeseporphyrin Dimers: functional Relevance to Oxygen Evolving Complex in PhotosystemII, Y. Naruta, Y. Shimazaki, F. Tani, E. I. Solomon, S. DeBeer Geroge, 4th International Conference on Porphyrins and Phthalocyanines (ICPP-4), 2-7/7/2006, Rome, Italy. Modeling Study of Dioxygen Activation in Cytochrome c Oxidase Active Site, Y. Naruta, Taiwan Bioinorganic Symposium 2006 (TBICS-2006), Taipei, ROC, 6-7/10/2006, Oxygen Activation with Bio-inspired Model Complexes Relating to cytochrome c Oxidase, Y, Naruta, Asian Bioinorganic Chemistry Symposium (AsBIC-3), 31/10-3/11/2006, Nanjin, China. Hydrogen Production with Renewable Energy, Y. Naruta, Green Sastainable Chemistry Lectures, JCII, 7/12/2006, Tokyo, Japan. Modeling Study of Oxygen Activation in Cytochrome c Oxidase: Roles of Residues at the Active Site, Y. Naruta, J.-G. Liu, X.-M. Ouyang, T. Chishiro, T. Higa, and F. Tani, 12th International conference in Bioinorganic Chemistry (ICBIC-12), Ann Arbor, USA, 31/7-5/8/2005. Dioxygen Activation Chemistry of Metalloenzymes and Models, Y. Naruta, PACIFICHEM-2005 (Symposium: Dioxygen Activation Chemistry of Metalloenzymes and Models), Honolulu, Hawaii, USA, 15-20/12/ Y. Naruta, Decomposition of Water: A Key for Hydrogen Economy in Collection of Lectures in Chemistry: Life and Living enriched by Elements, Kubapro, Tokyo 2006 pp

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