1998 年度実績報告書

溶液内における金属イオンの動態の解明と動的分析化学への展開

研究課題

研究課題/領域番号	10440221
研究種目	基盤研究(B)
研究機関	名古屋大学
研究代表者	舟橋重信名古屋大学, 大学院・理学研究科, 教授 (30022700)
研究分担者	稲田康宏名古屋大学, 物質科学国際研究センター, 助手 (60242814) 高木秀夫名古屋大学, 大学院・理学研究科, 助教授 (70242807)
キーワード	動態解明 / 金属イオン / 溶媒和構造 / 溶媒交換反応 / シクロパラデーション反応 / メタロポルフィリン / 外圏型電子移動反応 / 短寿命反応中間体
研究概要	本研究では、時々刻々変化(反応)している系の構成物質を分析することが可能な方法論を開拓し、反応時間というもう一つの次元を導入することによって、分析の感度と選択性を飛躍的に高めると同時に、このような、いわば“動的分析化学"といえる新しい分野を開拓することを目的としている。このために、溶液内分析化学反応の機構論的研究を系統的に遂行し、その反応動態の分析化学的見地での評価を行った。 (1) 各種溶媒中における金属イオンの溶媒交換反応と溶媒特性による反応性の差異に関しては、EX-AFS法を用いて様々な非水溶媒中における金属イオンの溶媒和構造を決定し、また、NMR法を用いて溶媒交換反応の活性化パラメーターを測定した。これにより、溶媒分子のかさ高さによる溶媒和構造の変化とその溶媒交換反応機構への影響を解明した。 (2) 立体特性を持つ配位子との錯形成反応機構の解明に関しては、ポルフィリンのメタレーション反応とシクロパラデーション反応のメカニズムを詳細に解明し、金属イオンの速度論的分析法の確立とより高い選択性の発現に向けての重要な情報を得た。 (3) 電子移動反応の機構と酸化還元反応に及ぼす触媒作用の解明に関しては、各種錯体間の電子移動反応速度を均一溶液中ならびに電極表面において測定し、錯体内部の構造変化に要するエネルギーが外圏型電子移動反応の活性化に至る過程を支配していることを明らかにした。 (4) 短寿命反応中間体の構造化学的研究に関連しては、高精度の時間分解EXAFSスペクトルをより短時間で測定するための放射光を光源とするエネルギー分散型光学系を備えた時間分解EXAFS装置の開発に着手した。

研究成果

(19件)

すべてその他

すべて文献書誌 (19件)

[文献書誌] Y.Inada: "Solvation Structures of Mn(II),Fe(II),Co(II),Ni(II),Cu(II),Zn(II),and Ga(III) Ions in Methanol,Ethanol,Dimethyl Sulfoxide,and Trimethylphoshate As Studied by EXAFS and Electronic Spectroscopies" The Journal of Physical Chemistry. (in press). (1999)
[文献書誌] Y.Tsutsui: "Reaction Mechanism of Water Exchange on Di- and Trivalent Cations of the First Transition Series and Structural Stability of Seven-Coordinate Species" Journal of Molecular Structure. (in press). (1999)
[文献書誌] Y.Inada: "Solvation Structure of Copper(I)Ion in Nonaqueous Solvents As Studied by EXAFS and ab Initio Molecular Orbital Methods" Zeitschrift fur Naturforschung B. (in press). (1999)
[文献書誌] S.Funahashi: "Solvation Structures of Metal Ions in Non-Aqueous Solvents As Studied by Means of EXAFS Spectroscopy" Trends in Inorganic Chemistry. (in press). (1998)
[文献書誌] T.Yagyu: "Electronic Effect of Substituents on Cyclopalladation of the Solvated Palladium(II)Complexes with N-Benzyl Triamine [Pd(Sol)(4-XC_6H_4CH_2)NH(CH_2)_3NR(CH_2)_3NH_2]^<2+> (Sol=Solvent;R=Ph,H,and Ne;X=H,Et,Me,MeO,Cl,and NO_2)" Bulletin of the Chemical Society of Japan. 71・8. 1857-1862 (1998)
[文献書誌] M.Matsumoto: "Electrochemical at Studies at Elevated Pressures: Reaction Volumes of Some Fe(III/II),Co(III/II),and Ni(III/II)Couples in Aqueous Solution and in Acetonitrille" The Review of High Pressure Science and Technology. 8・7. 1262-1264 (1998)
[文献書誌] Y.Tsutsui: "The Structural Stability of Seven-Coordinate Species Relevant to Mechanism of Water-Exchange Reaction" Bulletin of the Chemical Society of Japan. 71・8. 1771-1779 (1998)
[文献書誌] T.Usui: "Investigation of the Thermal Inversion Rates of Azobenzenes in Supercritical and Gaseous CO_2: A Shift from the Energy-Transfer-Limited to the TST-Valid Region at Low Densities" Chemistry Letters. 11. 1159-1160 (1998)
[文献書誌] K.Kashiwabara: "Synthesis and Structural Characterization of Cobalt(III)Complexes of Hybrid Donor-Type Didentate and Tetradentate Ligands Bearing Dimethlphosphino and Thioether Groups" Polyhedron. 17・11-12. 1817-1829 (1998)
[文献書誌] T.Yagyu: "Mechanistic Studies on Cyclopalladation of the Solvated Palladium(II) Complexes with N-Benzyl Triamine Ligands. Crystal Structures of [Pd(S)(Bn_2Medptn)](BF_4)_2(S=Acetonitrile and N,N-Dimethylformamide;Bn_2Medptn=N,N"-Dibenzyl-N'-methyl-3,3'-diaminodipropylamine)and[Bn_2Medptn-C,N,N',N")]CF_3SO_3" Bulletin of the Chemical Society of Japan. 71・3. 619-629 (1998)
[文献書誌] K.Kato: "Variable-Temperature and-Pressure Kinetic Study of the Complexation of the Beryllium(II)Ion with 2-Amino-2,4,6-cycloheptatrien-1-one in N,N-Dimethlformamide" Main Group Chemistry. 2. 215-219 (1998)
[文献書誌] Y.Inada: "Development of Time-Resolved Stopped-Flow EXAFS Apparatus and Structure Determination of Short-Lived Reaction Intermediates Formed in Dynamic Process of Inorganic Reactions Solution" Recent Research Developments in Pure & Applied Chemistry. 2. 347-359 (1998)
[文献書誌] Y.Inada: "Formation and Deprotonation Kinetics of the Sitting-Atop Complex of the Copper(II)Ion with 5,10,15,20-Tetraphenylporphyrin Relevant to Porphyrin Metalation Mechanism. Structure of Copper(II)-Pyridine Complexes in Acetonitrile as Determined by EXAFS Spectroscopy" Inorganic Chemistry. 37・21. 5519-5526 (1998)
[文献書誌] Y.Inada: "Measurements of Fast Reactions in Solution by the Stopped-Flow Technique" Bunseki. 9. 647-654 (1998)
[文献書誌] Y.Inada: "Solvation Structures and Kinetics of Solvent Exchange Reactions of the Manganese(II)Ion in Six Nitriles As Studied by X-ray Diffraction,EXAFS,and NMR Techniques" Inorganic Chemistry. 37・8. 1886-1891 (1998)
[文献書誌] H.D.Takagi: "Electron Transfer Reactions at Elevated Pressures" The Review of High Pressure Science and Technology. 8・3. 193-208 (1998)
[文献書誌] Y.Kuchiyama: "Kinetics of the Oxidation Reaction of Bis(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)copper(I)by Bis(1,4,7-triazacyclononane)nickel(III)in Acetonitrile" Inorganica Chimica Acta. 227・1. 31-36 (1998)
[文献書誌] Y.Tsutsui: "The Stability of Seven-Coordinate Species Earlier Members in the First Transition Series: Heptahydrated Ti(II),V(II),Cr(II),and Mn(II)Ions Relevant to an Intermediate or a Transition State in Water-Exchange Reaction" Bulletin of the Chemical Society of Japan. 71・1. 73-78 (1998)
[文献書誌] 舟橋重信: "無機溶液反応の化学" 裳華房, 271 (1998)

1998 年度 実績報告書

溶液内における金属イオンの動態の解明と動的分析化学への展開

研究代表者

舟橋 重信 名古屋大学, 大学院・理学研究科, 教授 (30022700)

研究成果

[文献書誌] Y.Inada: "Solvation Structures of Mn(II),Fe(II),Co(II),Ni(II),Cu(II),Zn(II),and Ga(III) Ions in Methanol,Ethanol,Dimethyl Sulfoxide,and Trimethylphoshate As Studied by EXAFS and Electronic Spectroscopies" The Journal of Physical Chemistry. (in press). (1999)

[文献書誌] Y.Tsutsui: "Reaction Mechanism of Water Exchange on Di- and Trivalent Cations of the First Transition Series and Structural Stability of Seven-Coordinate Species" Journal of Molecular Structure. (in press). (1999)

[文献書誌] Y.Inada: "Solvation Structure of Copper(I)Ion in Nonaqueous Solvents As Studied by EXAFS and ab Initio Molecular Orbital Methods" Zeitschrift fur Naturforschung B. (in press). (1999)

[文献書誌] S.Funahashi: "Solvation Structures of Metal Ions in Non-Aqueous Solvents As Studied by Means of EXAFS Spectroscopy" Trends in Inorganic Chemistry. (in press). (1998)

[文献書誌] M.Matsumoto: "Electrochemical at Studies at Elevated Pressures: Reaction Volumes of Some Fe(III/II),Co(III/II),and Ni(III/II)Couples in Aqueous Solution and in Acetonitrille" The Review of High Pressure Science and Technology. 8・7. 1262-1264 (1998)

[文献書誌] Y.Tsutsui: "The Structural Stability of Seven-Coordinate Species Relevant to Mechanism of Water-Exchange Reaction" Bulletin of the Chemical Society of Japan. 71・8. 1771-1779 (1998)

[文献書誌] T.Usui: "Investigation of the Thermal Inversion Rates of Azobenzenes in Supercritical and Gaseous CO_2: A Shift from the Energy-Transfer-Limited to the TST-Valid Region at Low Densities" Chemistry Letters. 11. 1159-1160 (1998)

[文献書誌] K.Kashiwabara: "Synthesis and Structural Characterization of Cobalt(III)Complexes of Hybrid Donor-Type Didentate and Tetradentate Ligands Bearing Dimethlphosphino and Thioether Groups" Polyhedron. 17・11-12. 1817-1829 (1998)

[文献書誌] K.Kato: "Variable-Temperature and-Pressure Kinetic Study of the Complexation of the Beryllium(II)Ion with 2-Amino-2,4,6-cycloheptatrien-1-one in N,N-Dimethlformamide" Main Group Chemistry. 2. 215-219 (1998)

[文献書誌] Y.Inada: "Development of Time-Resolved Stopped-Flow EXAFS Apparatus and Structure Determination of Short-Lived Reaction Intermediates Formed in Dynamic Process of Inorganic Reactions Solution" Recent Research Developments in Pure & Applied Chemistry. 2. 347-359 (1998)

[文献書誌] Y.Inada: "Measurements of Fast Reactions in Solution by the Stopped-Flow Technique" Bunseki. 9. 647-654 (1998)

[文献書誌] Y.Inada: "Solvation Structures and Kinetics of Solvent Exchange Reactions of the Manganese(II)Ion in Six Nitriles As Studied by X-ray Diffraction,EXAFS,and NMR Techniques" Inorganic Chemistry. 37・8. 1886-1891 (1998)

[文献書誌] H.D.Takagi: "Electron Transfer Reactions at Elevated Pressures" The Review of High Pressure Science and Technology. 8・3. 193-208 (1998)

[文献書誌] Y.Kuchiyama: "Kinetics of the Oxidation Reaction of Bis(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)copper(I)by Bis(1,4,7-triazacyclononane)nickel(III)in Acetonitrile" Inorganica Chimica Acta. 227・1. 31-36 (1998)

[文献書誌] 舟橋 重信: "無機溶液反応の化学" 裳華房, 271 (1998)

1998 年度実績報告書

舟橋重信名古屋大学, 大学院・理学研究科, 教授 (30022700)

[文献書誌] 舟橋重信: "無機溶液反応の化学" 裳華房, 271 (1998)