2001 Fiscal Year Annual Research Report

複核金属錯体を用いる水の光酸化触媒の開発

Research Project

Project/Area Number	13440216
Research Institution	Osaka University
Principal Investigator	福住俊一大阪大学, 大学院・工学研究科, 教授 (40144430)
Co-Investigator(Kenkyū-buntansha)	末延知義大阪大学, 大学院・工学研究科, 助手 (90271030) 今堀博大阪大学, 大学院・工学研究科, 助教授 (90243261)
Keywords	光合成 / 水の4電子酸化 / 複核金属錯体 / 高原子価オキソ金属ポルフィリン / 光触媒 / 地球環境 / エネルギー問題 / 電子移動
Research Abstract	21世紀に地球環境およびエネルギー問題の危機の根本的解決を図るためには、水の効率的な酸化触媒を開発することが鍵となる。そこで本研究では、水の4電子酸化を達成するために高原子価二核鉄およびマンガンの基礎ポルフィリンカチオンラジカルを触媒活性中心とし、その生成に必要となる4つのルテニウム錯体を連結した複核金属錯体を用いて、水の触媒的光酸化を達成することを目的としている。高原子価鉄およびマンガンオキソポルフィリンはP450酵素反応にみられるように、生体内において基質酸化反応における酸化活性種として重要な役割を果たしている。これまでその生成は過酸化物などの強力な活性酸素種との反応によって行われてきたため電子移動特性について不明な点が多く残されていた。そこで今年度は金属ポルフィリンを電子移動酸化し、生成する不安定過渡種の同定を各種分光学的手法により行うことにより電子移動過程に関する系統的な検討を行った。また高原子価金属ポルフィリンが水を電子供給源とした反応の有効な触媒となることも見いだした。 (TMP)Mn^<III>(OH)(TMP=5,10,15,20-テトラキスメシチルポルフィリン)を電子移動酸化として高原子価Mn(IV)とし、水の酸化触媒作用について検討した。MeCn/H_2O(5:1 v/v)の混合溶媒中、水酸化テトラメチルアンモニウム(Me_4NOH)存在かにおいて(TMP)Mn^<III>(OH)をルテニウムトリス(2,2'-ビピリジン)(III)錯体[Ru(bpy)_3]^<3+>により酸化し[(TMP)Mn^<IV>(=O)]^<・+>を生成させたところ同時に酸素の発生が観測され、酸素の発生量は添加した酸化剤の1/4当量となった。また、このとき[Ru(bpy)_3]^<3+>の濃度の増加速度は[(TMP)Mn^<IV>(=O)]^<・+>濃度に対して二次の依存性を示して増大したので[(TMP)Mn^<IV>(=O)]^<・+>のオキソ基のカップリングにより酸素が発生すると考えられる。従って、[(TMP)Mn^<IV>(=O)]^<・+>は水を四電子酸化し酸素を発生させる触媒として有効に機能することがわかった。

Research Products

(29 results)

All Other

All Publications (29 results)

[Publications] Shunichi Fukuzumi et al.: "Fine Tuning of the Interaction Between the Copper(I) and Disulfide Bond Formation of a Bis(m-thiolato)dicopper(II) Complex by Reductive Cleavage of the Disulfide Bond with Copper(I)"J. Am. Chem. Soc.. 123・17. 4087-4088 (2001)
[Publications] Shunichi Fukuzumi et al.: "C-H Bond Activation of External Substrates with a Bis(m-oxo)dicopper(III) Complex"J. Am. Chem. Soc.. 123・25. 6203-6204 (2001)
[Publications] Shunichi Fukuzumi et al.: "Charge Separation in a Novel Artificial Photosynthetic Reaction Center Lives 380ms"J. Am. Chem. Soc.. 123・27. 6617-6628 (2001)
[Publications] Shunichi Fukuzumi et al.: "Oxygenation of Phenols to Catechols by A (μ-η^2:η^2-peroxo)dicopper(II) Complex : Mechanistic Insight into the Phenolase Activity of Tyrosinase"J. Am. Chem. Soc.. 123・27. 6708-6709 (2001)
[Publications] Shunichi Fukuzumi et al.: "Change in Spin State and Enhancement of Redox Reactivity of Photoexcited States of Aromatic Carbonyl Compounds by Complexation with Metal Ion Salts Acting as Lewis Acids. Lewis Acid-Catalyzed Photoaddition of Benzyltrimethylsilane and Tetramethyltin via Photoinduced Electron Transfer"J. Am. Chem. Soc.. 123・32. 7756-7766 (2001)
[Publications] Shunichi Fukuzumi et al.: "Photoalkylation of 10-Alkylacridinium Ion via a Charge-Shift Type of Photoinduced Electron Transfer Controlled by Solvent Polarity"J. Am. Chem. Soc.. 123・35. 8459-8467 (2001)
[Publications] Shunichi Fukuzumi et al.: "Metal Ion-Catalyzed Cycloaddition vs Hydride Transfer Reactions of NADH Analogues with ρ-Benzoquinones"J. Am. Chem. Soc.. 123・42. 10191-10199 (2001)
[Publications] Shunichi Fukuzumi et al.: "Photochemical and Electrochemical Properties of Zinc Chlorin-C_<60>, Dyad as Compared to Corresponding Free-Base Chlorin-C_<60>, Free-Base Porphyrin-C_<60> and Zinc Porphyrin-C_<60> Dyads"J. Am. Chem. Soc.. 123・43. 10676-10683 (2001)
[Publications] Shunichi Fukuzumi et al.: "Formation, Characterization, and Reactivity of Bis(μ-oxo)dinickel(III) Complexes Supported by A Series of Bis[2-(2-pyridyl)ethyl]amine Ligands"J. Am. Chem. Soc.. 123・45. 11168-11178 (2001)
[Publications] Shunichi Fukuzumi et al.: "Extremely Slow Long-Range Electron Transfer Reactions Across Zeolite-Solution Interface"J. Am. Chem. Soc.. 123・45. 11331-11332 (2001)
[Publications] Shunichi Fukuzumi et al.: "Scandium Ion-Promoted Photoinduced Electron-Transfer Oxidation of Fullerenes and Derivatives by p-Chloranil and p-Benzoquinone"J. Am. Chem. Soc.. 123・50. 12458-12465 (2001)
[Publications] Shunichi Fukuzumi et al.: "Large Photocurrent Generation of Gold Eelectrodes Modified with [60]Fullerene-Linked Oligothiophenes Bearing a Tripodal Rigid Anchor"J. Am. Chem. Soc.. 124・4. 532-533 (2002)
[Publications] Shunichi Fukuzumi et al.: "Oxo-transfer Reaction from A Bis(μ-oxo)dicopper(III) Complex"J. Am. Chem. Soc.. 124・6. 998-1002 (2002)
[Publications] Shunichi Fukuzumi et al.: "Efficient Catalysis of Rare-Earth Metal Ions in Photoinduced Electron-Transfer Oxidation of Benzyl Alcohols by a Flavin Analogue"J. Phys. Chem. Soc.. 105・46. 10501-10510 (2002)
[Publications] Shunichi Fukuzumi et al.: "Electron Transfer Properties of Singlet Oxygen and Promoting Effects of Scandium Ion"J. Phys. Chem. Soc.. 106・7. 1241-1247 (2002)
[Publications] Shunichi Fukuzumi et al.: "Dehydrogenation vs Oxygenation in Photosensitized Oxidation of 9-Substituted 10-Methyl-9, 10-dihydroacridine in the Presence of Scandium Ion"J. Phys. Chem. Soc.. 106・7. 1465-1472 (2002)
[Publications] Shunichi Fukuzumi et al.: "Characterization of Imidazolate-Bridged Dinuclear and Mononuclear Hydroperoxo Complexes"Inorg. Chem. 40・13. 3200-3207 (2001)
[Publications] Shunichi Fukuzumi et al.: "Modulation of Coordination Chemistry in Copper(I) Complexes Supported by Bis[2-(2-pyridyl)ethyl]amine-based Tridentate Ligands"Inorg. Chem. 40・26. 6604-6609 (2001)
[Publications] Shunichi Fukuzumi et al.: "Spectroscopy and Photocurrent Generation in Nanostructured Thin Films of Porphyrin-Fullerene Dyad Clusters"Chem. Lett. 784-785 (2001)
[Publications] Shunichi Fukuzumi et al.: "Quantitative Evaluation of Lewis Acidity of Zinc Ion with Tetradentate Tripodal Ligands in Formation of the Superoxide Complexes"Chem. Lett. 920-921 (2001)
[Publications] Shunichi Fukuzumi et al.: "Evaluation of Lewis Acidity of Organotin compounds and the Catalytic Reactivity in Electron Transfer"Chem. Lett. 978-979 (2001)
[Publications] Shunichi Fukuzumi et al.: "Superoxide Anion Generation via Electron-Transfer Oxidation of Catechin Dianion by Molecular Oxygen in an Aprotic Medium"Chem. Lett. 1152-1153 (2001)
[Publications] Shunichi Fukuzumi et al.: "Coordination of Semiquinone and Superoxide Radical Anions to the Zinc Ion in SOD Model Complexes that Act as the Key Step in Disproportionation of the Radical Anions"Chem. Eur. J.. 7・22. 4947-4953 (2001)
[Publications] Shunichi Fukuzumi et al.: "Concentration Effects of Porphyrin Monolayers on the Structure and Photoelectrochemical Properties of Mixed Self-Assembled Monolayers of Porphytin and Alkanethiol on Gold Electrodes"Langmuir. 17・16. 4925-4931 (2001)
[Publications] Shunichi Fukuzumi et al.: "Porphyrin Monolayer-Modified Gold Clusters as Photoactive Materials"Adv. Mater. 13・15. 1197-1199 (2001)
[Publications] Shunichi Fukuzumi et al.: "Charge-transfer emission of compact porphyrin-fullerene dyad analyzed by Marcus theory of electron-transfer"Spectrochim. Acta Part A. 57. 2229-2244 (2001)
[Publications] Shunichi Fukuzumi et al.: "Evidence that gold(III) porphyrins are not electrochemically inert : facile generation of gold(II) 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)porphyrin"Chem. Commun.. 356-357 (2002)
[Publications] Shunichi Fukuzumi et al.: "Thermal Intramolecular Electron Transfer in a Ferrocene-Naphthoquinone Linked Dyad Promoted by Metal Ion"Angew. Chem. Int. Ed.. 41・4. 620-622 (2002)
[Publications] Shunichi Fukuzumi et al.: "Fullerenes 2001-Volume 11. (Proceedings of the Eighth International Symposium of the 197th Meeting of The Electrochemical Society)"The Electrochemical Society, INC.. 69 (2001)

2001 Fiscal Year Annual Research Report

複核金属錯体を用いる水の光酸化触媒の開発

Principal Investigator

福住 俊一 大阪大学, 大学院・工学研究科, 教授 (40144430)

Research Products

[Publications] Shunichi Fukuzumi et al.: "Fine Tuning of the Interaction Between the Copper(I) and Disulfide Bond Formation of a Bis(m-thiolato)dicopper(II) Complex by Reductive Cleavage of the Disulfide Bond with Copper(I)"J. Am. Chem. Soc.. 123・17. 4087-4088 (2001)

[Publications] Shunichi Fukuzumi et al.: "C-H Bond Activation of External Substrates with a Bis(m-oxo)dicopper(III) Complex"J. Am. Chem. Soc.. 123・25. 6203-6204 (2001)

[Publications] Shunichi Fukuzumi et al.: "Charge Separation in a Novel Artificial Photosynthetic Reaction Center Lives 380ms"J. Am. Chem. Soc.. 123・27. 6617-6628 (2001)

[Publications] Shunichi Fukuzumi et al.: "Oxygenation of Phenols to Catechols by A (μ-η^2:η^2-peroxo)dicopper(II) Complex : Mechanistic Insight into the Phenolase Activity of Tyrosinase"J. Am. Chem. Soc.. 123・27. 6708-6709 (2001)

[Publications] Shunichi Fukuzumi et al.: "Photoalkylation of 10-Alkylacridinium Ion via a Charge-Shift Type of Photoinduced Electron Transfer Controlled by Solvent Polarity"J. Am. Chem. Soc.. 123・35. 8459-8467 (2001)

[Publications] Shunichi Fukuzumi et al.: "Metal Ion-Catalyzed Cycloaddition vs Hydride Transfer Reactions of NADH Analogues with ρ-Benzoquinones"J. Am. Chem. Soc.. 123・42. 10191-10199 (2001)

[Publications] Shunichi Fukuzumi et al.: "Photochemical and Electrochemical Properties of Zinc Chlorin-C_<60>, Dyad as Compared to Corresponding Free-Base Chlorin-C_<60>, Free-Base Porphyrin-C_<60> and Zinc Porphyrin-C_<60> Dyads"J. Am. Chem. Soc.. 123・43. 10676-10683 (2001)

[Publications] Shunichi Fukuzumi et al.: "Formation, Characterization, and Reactivity of Bis(μ-oxo)dinickel(III) Complexes Supported by A Series of Bis[2-(2-pyridyl)ethyl]amine Ligands"J. Am. Chem. Soc.. 123・45. 11168-11178 (2001)

[Publications] Shunichi Fukuzumi et al.: "Extremely Slow Long-Range Electron Transfer Reactions Across Zeolite-Solution Interface"J. Am. Chem. Soc.. 123・45. 11331-11332 (2001)

[Publications] Shunichi Fukuzumi et al.: "Scandium Ion-Promoted Photoinduced Electron-Transfer Oxidation of Fullerenes and Derivatives by p-Chloranil and p-Benzoquinone"J. Am. Chem. Soc.. 123・50. 12458-12465 (2001)

[Publications] Shunichi Fukuzumi et al.: "Large Photocurrent Generation of Gold Eelectrodes Modified with [60]Fullerene-Linked Oligothiophenes Bearing a Tripodal Rigid Anchor"J. Am. Chem. Soc.. 124・4. 532-533 (2002)

[Publications] Shunichi Fukuzumi et al.: "Oxo-transfer Reaction from A Bis(μ-oxo)dicopper(III) Complex"J. Am. Chem. Soc.. 124・6. 998-1002 (2002)

[Publications] Shunichi Fukuzumi et al.: "Efficient Catalysis of Rare-Earth Metal Ions in Photoinduced Electron-Transfer Oxidation of Benzyl Alcohols by a Flavin Analogue"J. Phys. Chem. Soc.. 105・46. 10501-10510 (2002)

[Publications] Shunichi Fukuzumi et al.: "Electron Transfer Properties of Singlet Oxygen and Promoting Effects of Scandium Ion"J. Phys. Chem. Soc.. 106・7. 1241-1247 (2002)

[Publications] Shunichi Fukuzumi et al.: "Dehydrogenation vs Oxygenation in Photosensitized Oxidation of 9-Substituted 10-Methyl-9, 10-dihydroacridine in the Presence of Scandium Ion"J. Phys. Chem. Soc.. 106・7. 1465-1472 (2002)

[Publications] Shunichi Fukuzumi et al.: "Characterization of Imidazolate-Bridged Dinuclear and Mononuclear Hydroperoxo Complexes"Inorg. Chem. 40・13. 3200-3207 (2001)

[Publications] Shunichi Fukuzumi et al.: "Modulation of Coordination Chemistry in Copper(I) Complexes Supported by Bis[2-(2-pyridyl)ethyl]amine-based Tridentate Ligands"Inorg. Chem. 40・26. 6604-6609 (2001)

[Publications] Shunichi Fukuzumi et al.: "Spectroscopy and Photocurrent Generation in Nanostructured Thin Films of Porphyrin-Fullerene Dyad Clusters"Chem. Lett. 784-785 (2001)

[Publications] Shunichi Fukuzumi et al.: "Quantitative Evaluation of Lewis Acidity of Zinc Ion with Tetradentate Tripodal Ligands in Formation of the Superoxide Complexes"Chem. Lett. 920-921 (2001)

[Publications] Shunichi Fukuzumi et al.: "Evaluation of Lewis Acidity of Organotin compounds and the Catalytic Reactivity in Electron Transfer"Chem. Lett. 978-979 (2001)

[Publications] Shunichi Fukuzumi et al.: "Superoxide Anion Generation via Electron-Transfer Oxidation of Catechin Dianion by Molecular Oxygen in an Aprotic Medium"Chem. Lett. 1152-1153 (2001)

[Publications] Shunichi Fukuzumi et al.: "Coordination of Semiquinone and Superoxide Radical Anions to the Zinc Ion in SOD Model Complexes that Act as the Key Step in Disproportionation of the Radical Anions"Chem. Eur. J.. 7・22. 4947-4953 (2001)

[Publications] Shunichi Fukuzumi et al.: "Concentration Effects of Porphyrin Monolayers on the Structure and Photoelectrochemical Properties of Mixed Self-Assembled Monolayers of Porphytin and Alkanethiol on Gold Electrodes"Langmuir. 17・16. 4925-4931 (2001)

[Publications] Shunichi Fukuzumi et al.: "Porphyrin Monolayer-Modified Gold Clusters as Photoactive Materials"Adv. Mater. 13・15. 1197-1199 (2001)

[Publications] Shunichi Fukuzumi et al.: "Charge-transfer emission of compact porphyrin-fullerene dyad analyzed by Marcus theory of electron-transfer"Spectrochim. Acta Part A. 57. 2229-2244 (2001)

[Publications] Shunichi Fukuzumi et al.: "Evidence that gold(III) porphyrins are not electrochemically inert : facile generation of gold(II) 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)porphyrin"Chem. Commun.. 356-357 (2002)

[Publications] Shunichi Fukuzumi et al.: "Thermal Intramolecular Electron Transfer in a Ferrocene-Naphthoquinone Linked Dyad Promoted by Metal Ion"Angew. Chem. Int. Ed.. 41・4. 620-622 (2002)

[Publications] Shunichi Fukuzumi et al.: "Fullerenes 2001-Volume 11. (Proceedings of the Eighth International Symposium of the 197th Meeting of The Electrochemical Society)"The Electrochemical Society, INC.. 69 (2001)

福住俊一大阪大学, 大学院・工学研究科, 教授 (40144430)