1999 Fiscal Year Annual Research Report

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

Research Project

Project/Area Number	10440221
Research Institution	Nagoya University
Principal Investigator	舟橋重信名古屋大学, 大学院・理学研究科, 教授 (30022700)
Co-Investigator(Kenkyū-buntansha)	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)
Keywords	動態解明 / 溶媒和構造 / 混合溶媒和化学種 / 外圏型電子移動反応 / 不安定短寿命反応中間体 / 金属ポルフィリン錯体 / 超臨界二酸化炭素 / 動的分析化学
Research Abstract	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、分析化学に反応時間の次元を導入することによって分析感度と選択性を高めると同時に、"動的分析化学"と言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、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)溶媒和構造と反応性との関係に関して、NMR法を用いて非配位性溶媒中に存在するBe^<2+>およびAl^<3+>イオンの混合溶媒和化学種のスペシエーションを行い、非経験的分子軌道計算と合わせて、配位子と金属イオンの大きさによる錯体構造の変化や金属―配位子間結合の特性を系統的に明らかにした。 (2)速度論的分析法における触媒作用の解明に関して、種々の金属(II,III)錯体間の外圏型電子移動反応速度を系統的に測定し、速度および機構に対する内配位圏の構造変化に由来するエネルギー因子を明らかにした。 (3)不安定短寿命中間体の構造解析に関して、エネルギー分散型光学系を有する放射光を光源として時間分解EXAFSビームラインの開発に着手し、電子移動前駆中間体の構造解析を行った。 (4)分析化学反応の反応機構解明に関して、アセトニトリル中における金属ポルフィリン錯体生成反応速度を測定し、SAT中間体の構造や物性を解明し、一般的なメタレーション機構を分子論的に解明した。 (5)動的分析化学のための方法論の開発として、超臨界二酸化炭素溶液間の迅速混合によって開始する化学反応の速度を測定することが可能な超臨界二酸化炭素用ストップトフロー装置を開発し、金属ポルフィリン錯体生成反応速度の測定を行った。

Research Products
(15 results)

All Other

All Publications (15 results)

[Publications] Y.Inada, Y.Itoh, S.Funahashi: "Mechanistic Studies on Solvent Exchange of Tetrahedrally Solvated Cobalt(II) Ion in 1,1,3,3-Tetramethylurea as a Bulky Solvent"Inorganic Reaction Mechanism. (in press). (2000)
[Publications] Y.Inada, S.Funahashi: "Equilibrium and Structural Study of Complexation of Iron(III) Ion with Chloride in Acidic Aqueous Solution by Means of X-Ray Absorption Spectroscopy"Zeitschrift fur Naturforschung B. (in press). (2000)
[Publications] M.Matsumoto, H.Kodama, S.Funahashi, and H.D.Takagi: "Reduction and Oxidation Reactions of Tetrakis(acetylacetonato)cerium(IV )and -(III) Complexes in Acetonitrile: Change in the Reaction Pathways with the Driving Force of the Reaction"Inorganic Reaction Mechanism. (in press). (2000)
[Publications] N.Koshino, Y.Kuchiyama, H.D.Takagi, and S.Funahashi: "Outer-Sphere Electron Transfer Reactions of Bis(2,9-dialkyl-1,10-phenanthroline) copper(II/I) in Acetonitrile: Alkyl=Methyl and Phenyl"Inorganic Reaction Mechanism. (in press). (2000)
[Publications] Y.Inada, H.Hayashi, K.Sugimoto, S.Funahashi: "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 Trimethylphosphate"The Journal of Physical Chemistry. 103・10. 1401-1406 (1999)
[Publications] N.Koshino, Y.Kuchiyama, H.Ozaki, S.Funahashi,and H.D.Takagi: "An Interpretation of Gated Behavior: Kinetic Studies of the Oxidation and Reduction Reactions of Bis(2,9-dimethy1-1,10-phenanthroline )copper(I/II) in Acetonitrile"Inorganic Chemistry. 38・14. 3352-3360 (1999)
[Publications] M.Matsumoto, M.Itoh, S.Funahashi, and H.D.Takagi: "Electron Transfer Reactions of Bis(1,4,7-trithiacyclononane) palladium(III/II), -platinum(III/II), and -gold(III/II) Complexes in Aqueous Solution and in Acetonitrile"Canadian Journal of Chemistry. 77. 1638-1647 (1999)
[Publications] N.Koshino, Y.Kuchiyama, S.Funahashi, and H.D.Takagi: "Electron Self-Exchange, Oxidation, and Reduction Reactions of Bis(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) copper(II/I) and Bis(6,6'-dimethyl-2,2'-bipyridine) copper(II/I) Couples in Acetonitrile"Canadian Journal of Chemistry. 77. 1498-1507 (1999)
[Publications] M.Matsumoto, S.Funahashi, and H.D.Takagi: "Electrochemical Electron Transfer reactions of M(ttcn)_2^<3+/2+> (M=Co,Pd,Pt,Au; ttcn=1,4,7-trithiacyclononane): the Relation of Reaction Volumes and Electron Transfer Rate Constants"Zeitschrift fur Naturforschung B. 54. 1138-1146 (1999)
[Publications] Y.Tsutsui, H.Wasada, and S.Funahashi: "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 (Theoretical Chemistry). 461-462. 379-390 (1999)
[Publications] Y.Inada, Y.Tsutsui, H.Wasada, S.Funahashi: "Solvation Structure of Copper(I) Ion in Nonaqueous Solvents As Studied by EXAFS and ab Initio Molecular Orbital Methods"Zeitschrift fur Naturforschung B. 54・2. 193-199 (1999)
[Publications] N.Koshino, Y.Kuchiyama. S.Funahashi,and H.D.Takagi: "Free Energy Barrier of Gated Electron Transfer Reactions: Reduction and Oxidation Reactions of Cu(6,6'-dimethyl-2,2'-bipyridine)_2^<2+/+>with Ru(hexafluoroacetylacetone)_3^<0/->"Chemical Physics Letters. 306. 291-296 (1999)
[Publications] H.D.Takagi, A.Takahashi, S.Iwatsuki, H.Hayashi, S.Funahashi,and K.Ogiyama: "An Investigation of the Photodegradation of Tetraphenyltin (IV) in THF"Phosphorus, Sulfur and Silicon. 150-151. 245-250 (1999)
[Publications] Y.Kanekiyo, S.Aizawa, N.Koshino, and S.Funahashi: "Complexation Equilibria of Oxy-acid-2-Amino-2-deoxy-D-gluconic acid-Metal Ion Ternary Systems in Aqueous Solution As Studied by Potentiometry. Binding Characteristics of Borate and Germanate"Inorganic Chimica Acta. 298/2. 154-164 (1999)
[Publications] 舟橋重信: "大学院錯体化学"講談社サイエンティフィク(印刷中). (2000)

1999 Fiscal Year Annual Research Report

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

Principal Investigator

舟橋 重信 名古屋大学, 大学院・理学研究科, 教授 (30022700)

Research Products

[Publications] Y.Inada, Y.Itoh, S.Funahashi: "Mechanistic Studies on Solvent Exchange of Tetrahedrally Solvated Cobalt(II) Ion in 1,1,3,3-Tetramethylurea as a Bulky Solvent"Inorganic Reaction Mechanism. (in press). (2000)

[Publications] Y.Inada, S.Funahashi: "Equilibrium and Structural Study of Complexation of Iron(III) Ion with Chloride in Acidic Aqueous Solution by Means of X-Ray Absorption Spectroscopy"Zeitschrift fur Naturforschung B. (in press). (2000)

[Publications] M.Matsumoto, H.Kodama, S.Funahashi, and H.D.Takagi: "Reduction and Oxidation Reactions of Tetrakis(acetylacetonato)cerium(IV )and -(III) Complexes in Acetonitrile: Change in the Reaction Pathways with the Driving Force of the Reaction"Inorganic Reaction Mechanism. (in press). (2000)

[Publications] N.Koshino, Y.Kuchiyama, H.D.Takagi, and S.Funahashi: "Outer-Sphere Electron Transfer Reactions of Bis(2,9-dialkyl-1,10-phenanthroline) copper(II/I) in Acetonitrile: Alkyl=Methyl and Phenyl"Inorganic Reaction Mechanism. (in press). (2000)

[Publications] Y.Inada, H.Hayashi, K.Sugimoto, S.Funahashi: "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 Trimethylphosphate"The Journal of Physical Chemistry. 103・10. 1401-1406 (1999)

[Publications] N.Koshino, Y.Kuchiyama, H.Ozaki, S.Funahashi,and H.D.Takagi: "An Interpretation of Gated Behavior: Kinetic Studies of the Oxidation and Reduction Reactions of Bis(2,9-dimethy1-1,10-phenanthroline )copper(I/II) in Acetonitrile"Inorganic Chemistry. 38・14. 3352-3360 (1999)

[Publications] M.Matsumoto, M.Itoh, S.Funahashi, and H.D.Takagi: "Electron Transfer Reactions of Bis(1,4,7-trithiacyclononane) palladium(III/II), -platinum(III/II), and -gold(III/II) Complexes in Aqueous Solution and in Acetonitrile"Canadian Journal of Chemistry. 77. 1638-1647 (1999)

[Publications] M.Matsumoto, S.Funahashi, and H.D.Takagi: "Electrochemical Electron Transfer reactions of M(ttcn)_2^<3+/2+> (M=Co,Pd,Pt,Au; ttcn=1,4,7-trithiacyclononane): the Relation of Reaction Volumes and Electron Transfer Rate Constants"Zeitschrift fur Naturforschung B. 54. 1138-1146 (1999)

[Publications] Y.Tsutsui, H.Wasada, and S.Funahashi: "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 (Theoretical Chemistry). 461-462. 379-390 (1999)

[Publications] Y.Inada, Y.Tsutsui, H.Wasada, S.Funahashi: "Solvation Structure of Copper(I) Ion in Nonaqueous Solvents As Studied by EXAFS and ab Initio Molecular Orbital Methods"Zeitschrift fur Naturforschung B. 54・2. 193-199 (1999)

[Publications] N.Koshino, Y.Kuchiyama. S.Funahashi,and H.D.Takagi: "Free Energy Barrier of Gated Electron Transfer Reactions: Reduction and Oxidation Reactions of Cu(6,6'-dimethyl-2,2'-bipyridine)_2^<2+/+>with Ru(hexafluoroacetylacetone)_3^<0/->"Chemical Physics Letters. 306. 291-296 (1999)

[Publications] H.D.Takagi, A.Takahashi, S.Iwatsuki, H.Hayashi, S.Funahashi,and K.Ogiyama: "An Investigation of the Photodegradation of Tetraphenyltin (IV) in THF"Phosphorus, Sulfur and Silicon. 150-151. 245-250 (1999)

[Publications] 舟橋重信: "大学院錯体化学"講談社サイエンティフィク(印刷中). (2000)

舟橋重信名古屋大学, 大学院・理学研究科, 教授 (30022700)