1991 年度実績報告書

錯体の電子状態と電子移動過程のダイナミックス

研究課題

研究課題/領域番号	03303005
研究機関	東北大学
研究代表者	荻野博東北大学, 理学部, 教授 (00004292)
研究分担者	谷口功熊本大学, 工学部, 教授 (90112391) 松村竹子奈良教育大学, 教育学部, 教授 (60031556) 田中晃二岡崎国立共同研究機構, 分子科学研究所, 教授 (00029274) 佐藤弦上智大学, 理工学部, 教授 (00053546) 佐々木陽一北海道大学, 理学部, 教授 (30004500)
キーワード	錯体 / 電子状態 / 電子移動 / ダイナミックス / 光合成 / トンネル顕微鏡 / エネルギ-ギャップ則 / 光誘起電荷分離
研究概要	錯体の電子状態ならびに電子移動過程のダイナミックスの両面で大きな研究上の進展があった。以下に成果をまとめる。 1.錯体の電子状態と酸化環元電位の相関関係について著しい進展があった。多くの新規ルテニウム錯体の合成に基づく測定が行われた。電位測定へのマイクロ電極の利用も行われた。複核錯体やクラスタ-(なかでも四核ー硫黄クラスタ-など)へも研究が拡張された。フェレドキシンのモデルとしての四鉄ー硫黄クラスタ-が取り上げられ、プロトン付加反応の解析、ミセルおよびポリマ-中に可溶化したクラスタ-の酸化環元挙動も詳細な解析が行われた。 2.固液界面での電子移動反応において吸着原子の生成をともなう反応を走査トンネル顕微鏡(STM)による原子レベルでの解明が行われ、STMによる研究がきわめて有用であり、今後益々重要になって行く見通しを得た。 3.単核錯体間の電子移動反応機構が研究され、ゼロ次反応則にしたがう特異な反応系も見出された。 4.フェレドキシン自体およびそのモデルクラスタ-の研究の進展により、電子伝達のダイナミックス測定および生体機能化学反応の追求への展望が開けた。 5.光合成電子移動機構を知るために適した分子の合成を系統的に行い、光合成電子移動の構造因子の解明が進んだ。 6.電子移動反応における理論的取り扱いが精力的に行われた。反応速度を制御する因子が詳細に検討され、エネルギ-ギャップ則や光誘起電荷分離反応の実験的知見に対する理論的理由づけが行われた。 7.全体の総括と情報交換のため、平成3年11月11日および12日に東工大百年記念館で公開シンポジウムを開催した。本シンポジウムには名古屋大学教養部の佐野充博士に招待講演「分子ヒステリシスとその周辺」も依頼し、ホットなトピックスとして有益な討論が行われた。

研究成果
(33件)

すべてその他

すべて文献書誌 (33件)

[文献書誌] Shinji Inomata: "Electrochemical behavior of[CP'_2Fe_2S_4]and[Cp'_2Fe_2S_4](PF_6)_2(Cp'=η^5ーC_5Me_5):Structural change of the Fe_2S_4 core accompanied by a change of redox state." Inorg.Chem.30. 3039-3043 (1991)
[文献書誌] Kei Unoura: "Kinetic studies of oxygen atom transfer reactions between various cisーdioxobis(dithiocarbamato)molybdenum(VI)complexes and triphenylphosphine." Bull.Chem.Soc.Jpn.64. 3372-3375 (1991)
[文献書誌] Shinji Inomata: "Synthesis and structure of mixedーligand ironーsulfur cubaneーlike clusters[(ηーC_5Me_5)_3(Ph_2C_2S_2)Fe_4S_5]^n(n=O and 1^+)" Inorg.Chem.31. (1992)
[文献書誌] M.Sugawara: "Effect of the membrane surface charge on the hostーguest complex of valinomycin in a synthetic lipid monolayer at the airーwater interface." Langmuir. 7. (1992)
[文献書誌] K.Odashima: "Biomembrane mimetic sensing chemistry" Trends in Analytical Chemistry. 10. 207-215 (1991)
[文献書誌] Y.Sasaki: "Preparation,Structure,and properties of the bis(μーacetato)(μーoxo)ruthenium(III) dimers,[Ru_2(μーCH_3COO)_3(μーO)(Py)_6]^<2+>and [Ru_2(μーCH_3COO)_2(μーO)(bpy)_2(py)_2]^<2+>." Inorg.Chem.30. 4903-4908 (1991)
[文献書誌] D.Akashi: "Preparation and electrochemical response of poly(4ーvinylpyridine)ーcoordinated oxoーacetato triruthenium cluster film." Chem.Lett.1992. 143-146 (1992)
[文献書誌] Kenji Sashikata: "In situ electrochemical scanning tunneling microscopy of singleーcrystal surfaces of Pt(III),Rh(III),and Pd(III)in aqueous sulfuric acid solution." J.Vacuum Science and Technology. B9. 457-464 (1991)
[文献書誌] Toshinori Hachiya: "Datailed underpotential deposition of copper on gold(111)in aqueous solutions." J.Electroanal.Chem.315. 275-291 (1991)
[文献書誌] Kenji Sashikata: "In situ scanning tunneling microscopy of underpotential deposition of copper on platinum(III)in sulfuric acid solutions." J.Electroanal.Chem.316. 361-368 (1991)
[文献書誌] N.Ishikawa: "Hole delocalization in naphthalocyaninatophthalocyaninatolutetium(III)." Chem.Phys.Lett.180. 51-56 (1991)
[文献書誌] Hirobumi Ushijima: "Effect of substituents and chalcogen atoms on the reduction halfーwave potentials of(substituted ηーcyclopentadienyl)(1,2ーsubstituted 1,2ーethylenedichalcogenolato)cobalt(III)complexes in acetonitnile solutions." J.Electroanal.Chem.303. 199-209 (1991)
[文献書誌] Yosimasa Hoshino: "Oxidative dehydrogenation of ethylenediamine coordinated to ruthenium with hexafluoroacetylacetonate,induced by electrochemical oxidation of ruthenium(II)to ruthenium(III)." Bull.Chem.Soc.Jpn.65. (1992)
[文献書誌] Y.Enomoto: "Monte Carlo simulation study on reorganization energy of electronーtransfer reactions in polar solution." Chem.Phys.Lett.178. 235-240 (1991)
[文献書誌] Y.Enomoto: "Monte Carlo simulation study on energy gap dependence of electron transfer reactions in polar solution:effect of electronic polarizability of solvent." Chem.Phys.Lett.186. 366-371 (1991)
[文献書誌] S.Nishikawa: "Determination of the bimolecular rate constant of photoinduced charge separation in the energy gap region where the reaction is diffusion controlledーanalysis of the transient effect in the course of fluorescence quenching reaction." Chem.Phys.Lett.185. 237-243 (1991)
[文献書誌] Nobutoshi Komeda: "Electrochemical carbon dioxide fixation to thioesters catalyzed by[Mo_2Fe_6S_8(SEt)_9]^<3->" J.Am.Chem.Soc.114. (1992)
[文献書誌] Koji Tanaka: "Electrochemical assimilatory and dissimilatory reductions of NO_3^ーand NO_2^ーvia a possible free NO intermediate." Inorg.Chem.30. 3282-3288 (1991)
[文献書誌] Koji Tanaka: "Redox potential of Fe_4S_4 cluster in hydrophobic and hydrophilic spheres." Bull.Chem.Soc.Jpn.64. 1192-1197 (1991)
[文献書誌] Hirotaka Nagao: "Carbon dioxide fixation competed with proton addition to methy acrylate." Chem.Lett.1991. 323-326 (1991)
[文献書誌] Toshio Tanaka: "Chemical simulation of the nitrogen cycle and the carbon dioxide fixation in microbial systems." Trends in Inorganic Chemistry. 1. 41-49 (1991)
[文献書誌] Masaーaki Haga: "Protonーinduced switching of metalーmetal interactions in dinuclear ruthenium and osmium complexed bridges by 2,2'ーbis(2ーpyridyl)bibenzimidazole." Inorg.Chem.30. 3843-3849 (1991)
[文献書誌] Takeshi Ohno: "A weak ΔGﾟdependence of back electron transfer within the geminate redox pairs formed in the quenching of excited ruthenium(II)complexes by methylviologen." J.Phys.Chem.95. 4723-4728 (1991)
[文献書誌] Takeshi Ohno: "Photoexcited sates of biーruthenium(II)compounds bridged by 2,2'ーbis(2ーpyridyl)bibenzimidazole or 1,2ーbis(2ー(2ーpyridyl)benzimidazolyl)ethane." Inorg.Chem.30. (1991)
[文献書誌] Y.Sakata: "Observation of large orientation effect on photoinduced electron transfer in rigid porphyrinーquinone compounds." Chem.Lett.1991. 1307-1310 (1991)
[文献書誌] B.Becker: "Ions derived from dianthrylethane species.How the mode of linking affects the intramolecular electron transfer." J.A.Chem.Soc.113. 1121-1127 (1991)
[文献書誌] T.Matsumura: "Relations between ^<13>CNMR and oxidation potentials of Ru(II)polypyridine complexes." Anal.Science. 7. (1991)
[文献書誌] K.Tsukahara: "Kinetics and mechanisms of the photoーinduced oxidation of ascorbic acid by molecular oxygen catalyzed by ruthenium(II)complexes containing 2,2'ーbipyridine and 2,2'ーbipyrazine." Bull.Chem.Soc.Jpn.64. 908-915 (1991)
[文献書誌] K.Kato: "Difference in Kinetic behavior on the photosensitized decomposition of the tris(oxalato)cobaltate(III)ion by tris(2,2'ーbipyridine)ruthenium(II)and bis(3,3'ーbiisoquinoline)(2,2'ーbipyridine)ruthenium(II)" Bull.Chem.Soc.Jpn.64. 1401-1403 (1991)
[文献書誌] S.YamasakiーNisida: "Kinetic studies of electronーtransfer reactions induced by the reductive quenching of tris(2,2'ーbipyridine)ruthenium(II)." Bull.Chem.Soc.Jpn.64. 1840-1845 (1991)
[文献書誌] S.YamasakiーNisida: "Kinetic studies on quenching reaction of the photoーexcited[Ru(bpy)_3]^<2+> with[Co(edta)]^- in the presence of EDTA,CDTA,and C_2O_4^<2->." Bull.Chem.Soc.Jpn.64. 1866-1871 (1991)
[文献書誌] M.Kimura: "Kinetics and mechanisms of photoーinduced reduction of iodine by diamineーNーpolycarboxylate ions in an aqueous solution." Bull.Chem.Soc.Jpn.64. 1872-1877 (1991)
[文献書誌] 富永昌人: "カ-ボン電極上でのペルオキシダ-ゼの電子移動反応" 分析化学. 40. 851-853 (1991)

1991 年度 実績報告書

錯体の電子状態と電子移動過程のダイナミックス

研究代表者

荻野 博 東北大学, 理学部, 教授 (00004292)

研究成果

[文献書誌] Shinji Inomata: "Electrochemical behavior of[CP'_2Fe_2S_4]and[Cp'_2Fe_2S_4](PF_6)_2(Cp'=η^5ーC_5Me_5):Structural change of the Fe_2S_4 core accompanied by a change of redox state." Inorg.Chem.30. 3039-3043 (1991)

[文献書誌] Kei Unoura: "Kinetic studies of oxygen atom transfer reactions between various cisーdioxobis(dithiocarbamato)molybdenum(VI)complexes and triphenylphosphine." Bull.Chem.Soc.Jpn.64. 3372-3375 (1991)

[文献書誌] Shinji Inomata: "Synthesis and structure of mixedーligand ironーsulfur cubaneーlike clusters[(ηーC_5Me_5)_3(Ph_2C_2S_2)Fe_4S_5]^n(n=O and 1^+)" Inorg.Chem.31. (1992)

[文献書誌] M.Sugawara: "Effect of the membrane surface charge on the hostーguest complex of valinomycin in a synthetic lipid monolayer at the airーwater interface." Langmuir. 7. (1992)

[文献書誌] K.Odashima: "Biomembrane mimetic sensing chemistry" Trends in Analytical Chemistry. 10. 207-215 (1991)

[文献書誌] Y.Sasaki: "Preparation,Structure,and properties of the bis(μーacetato)(μーoxo)ruthenium(III) dimers,[Ru_2(μーCH_3COO)_3(μーO)(Py)_6]^<2+>and [Ru_2(μーCH_3COO)_2(μーO)(bpy)_2(py)_2]^<2+>." Inorg.Chem.30. 4903-4908 (1991)

[文献書誌] D.Akashi: "Preparation and electrochemical response of poly(4ーvinylpyridine)ーcoordinated oxoーacetato triruthenium cluster film." Chem.Lett.1992. 143-146 (1992)

[文献書誌] Kenji Sashikata: "In situ electrochemical scanning tunneling microscopy of singleーcrystal surfaces of Pt(III),Rh(III),and Pd(III)in aqueous sulfuric acid solution." J.Vacuum Science and Technology. B9. 457-464 (1991)

[文献書誌] Toshinori Hachiya: "Datailed underpotential deposition of copper on gold(111)in aqueous solutions." J.Electroanal.Chem.315. 275-291 (1991)

[文献書誌] Kenji Sashikata: "In situ scanning tunneling microscopy of underpotential deposition of copper on platinum(III)in sulfuric acid solutions." J.Electroanal.Chem.316. 361-368 (1991)

[文献書誌] N.Ishikawa: "Hole delocalization in naphthalocyaninatophthalocyaninatolutetium(III)." Chem.Phys.Lett.180. 51-56 (1991)

[文献書誌] Hirobumi Ushijima: "Effect of substituents and chalcogen atoms on the reduction halfーwave potentials of(substituted ηーcyclopentadienyl)(1,2ーsubstituted 1,2ーethylenedichalcogenolato)cobalt(III)complexes in acetonitnile solutions." J.Electroanal.Chem.303. 199-209 (1991)

[文献書誌] Yosimasa Hoshino: "Oxidative dehydrogenation of ethylenediamine coordinated to ruthenium with hexafluoroacetylacetonate,induced by electrochemical oxidation of ruthenium(II)to ruthenium(III)." Bull.Chem.Soc.Jpn.65. (1992)

[文献書誌] Y.Enomoto: "Monte Carlo simulation study on reorganization energy of electronーtransfer reactions in polar solution." Chem.Phys.Lett.178. 235-240 (1991)

[文献書誌] Y.Enomoto: "Monte Carlo simulation study on energy gap dependence of electron transfer reactions in polar solution:effect of electronic polarizability of solvent." Chem.Phys.Lett.186. 366-371 (1991)

[文献書誌] S.Nishikawa: "Determination of the bimolecular rate constant of photoinduced charge separation in the energy gap region where the reaction is diffusion controlledーanalysis of the transient effect in the course of fluorescence quenching reaction." Chem.Phys.Lett.185. 237-243 (1991)

[文献書誌] Nobutoshi Komeda: "Electrochemical carbon dioxide fixation to thioesters catalyzed by[Mo_2Fe_6S_8(SEt)_9]^<3->" J.Am.Chem.Soc.114. (1992)

[文献書誌] Koji Tanaka: "Electrochemical assimilatory and dissimilatory reductions of NO_3^ーand NO_2^ーvia a possible free NO intermediate." Inorg.Chem.30. 3282-3288 (1991)

[文献書誌] Koji Tanaka: "Redox potential of Fe_4S_4 cluster in hydrophobic and hydrophilic spheres." Bull.Chem.Soc.Jpn.64. 1192-1197 (1991)

[文献書誌] Hirotaka Nagao: "Carbon dioxide fixation competed with proton addition to methy acrylate." Chem.Lett.1991. 323-326 (1991)

[文献書誌] Toshio Tanaka: "Chemical simulation of the nitrogen cycle and the carbon dioxide fixation in microbial systems." Trends in Inorganic Chemistry. 1. 41-49 (1991)

[文献書誌] Masaーaki Haga: "Protonーinduced switching of metalーmetal interactions in dinuclear ruthenium and osmium complexed bridges by 2,2'ーbis(2ーpyridyl)bibenzimidazole." Inorg.Chem.30. 3843-3849 (1991)

[文献書誌] Takeshi Ohno: "A weak ΔGﾟdependence of back electron transfer within the geminate redox pairs formed in the quenching of excited ruthenium(II)complexes by methylviologen." J.Phys.Chem.95. 4723-4728 (1991)

[文献書誌] Takeshi Ohno: "Photoexcited sates of biーruthenium(II)compounds bridged by 2,2'ーbis(2ーpyridyl)bibenzimidazole or 1,2ーbis(2ー(2ーpyridyl)benzimidazolyl)ethane." Inorg.Chem.30. (1991)

[文献書誌] Y.Sakata: "Observation of large orientation effect on photoinduced electron transfer in rigid porphyrinーquinone compounds." Chem.Lett.1991. 1307-1310 (1991)

[文献書誌] B.Becker: "Ions derived from dianthrylethane species.How the mode of linking affects the intramolecular electron transfer." J.A.Chem.Soc.113. 1121-1127 (1991)

[文献書誌] T.Matsumura: "Relations between ^<13>CNMR and oxidation potentials of Ru(II)polypyridine complexes." Anal.Science. 7. (1991)

[文献書誌] K.Tsukahara: "Kinetics and mechanisms of the photoーinduced oxidation of ascorbic acid by molecular oxygen catalyzed by ruthenium(II)complexes containing 2,2'ーbipyridine and 2,2'ーbipyrazine." Bull.Chem.Soc.Jpn.64. 908-915 (1991)

[文献書誌] K.Kato: "Difference in Kinetic behavior on the photosensitized decomposition of the tris(oxalato)cobaltate(III)ion by tris(2,2'ーbipyridine)ruthenium(II)and bis(3,3'ーbiisoquinoline)(2,2'ーbipyridine)ruthenium(II)" Bull.Chem.Soc.Jpn.64. 1401-1403 (1991)

[文献書誌] S.YamasakiーNisida: "Kinetic studies of electronーtransfer reactions induced by the reductive quenching of tris(2,2'ーbipyridine)ruthenium(II)." Bull.Chem.Soc.Jpn.64. 1840-1845 (1991)

[文献書誌] S.YamasakiーNisida: "Kinetic studies on quenching reaction of the photoーexcited[Ru(bpy)_3]^<2+> with[Co(edta)]^- in the presence of EDTA,CDTA,and C_2O_4^<2->." Bull.Chem.Soc.Jpn.64. 1866-1871 (1991)

[文献書誌] M.Kimura: "Kinetics and mechanisms of photoーinduced reduction of iodine by diamineーNーpolycarboxylate ions in an aqueous solution." Bull.Chem.Soc.Jpn.64. 1872-1877 (1991)

[文献書誌] 富永 昌人: "カ-ボン電極上でのペルオキシダ-ゼの電子移動反応" 分析化学. 40. 851-853 (1991)

1991 年度実績報告書

荻野博東北大学, 理学部, 教授 (00004292)

[文献書誌] 富永昌人: "カ-ボン電極上でのペルオキシダ-ゼの電子移動反応" 分析化学. 40. 851-853 (1991)