1991 Fiscal Year Annual Research Report

溶液の非平衡過程の分子論的アプロ-チ・反応活性種の構造

Research Project

Project/Area Number	03231105
Research Institution	Okazaki National Research Institutes
Principal Investigator	大瀧仁志岡崎国立共同研究機構, 分子科学研究所, 教授 (80022549)
Co-Investigator(Kenkyū-buntansha)	佐々木陽一北海道大学, 理学部, 教授 (30004500) 山口敏男福岡大学, 理学部, 助教授 (70158111) 舟橋重信名古屋大学, 理学部, 教授 (30022700)
Keywords	反応活性種 / 反応中間体 / 迅速EXAFS / 多核錯体 / 溶液X線回折 / 過冷却液体 / ストップド・フロ-
Research Abstract	本研究では、計画班員4名が分担・協力して反応活性種並びに反応中間体の構造について研究を進めた。さらに公募班員とも積極的に協同研究を展開した。大瀧・舟橋は、試料セルの窓材に窒化ホウ素を用いることによって、数百回のフロ-積算に耐えるセルの開発に成功し、これを付置した実験室スケ-ルの迅速EXAFS測定装置を開発した。そこで田端が研究を進めているメタロポルフィリンの金属イオンの置換反応時に存在すると推定されるヘテロ二核中間体の構造を本装置を用いて直接決定するため、平衡時に存在する各種のメタロポルフィリンのEXAFSスペクトルを測定した。舟橋は世界で初の高圧ストップト・フロ-NMR測定装置を開発した。またポルフィリン錯体の生成反応においては、ポルフィリン環の変形した活性種が存在することや、Ni(II)イオンのエチレンジアミン溶媒交換反応では、2分子のエチレンジアミンが単座で配位した6配位の中間体が存在することを推定した。佐々木は金属クラスタ-錯体の生成過程中に存在する中間体の役割を解明するため、2個のルテニウムイオンを含む新しい三核金属錯体Ru_2M(M=Mg,Mn,Fe)を合成し、ルテニウム二核錯体が三核錯体に変化する際の反応中間体の構造に関する知見を得た。山口はイメ-ジング・プレ-トを用いた読み取り装置を設置することにより、極めて短時間で液体・溶液のX線回折デ-タを得ることができる迅速X線回折装置を完成した。また、新しく開発したin‐situ電気化学セルを用いて、蛍光EXAFS法により、光化学SPIIのモデルとしてのマンガン(III,IV)化合物の構造を明らかにした。上記の研究は、公募班員とも協力して進めることができ、本年度の研究は、当初の計画通り遂行できた。

Research Products

(34 results)

All Other

All Publications (34 results)

[Publications] K.Waizumi: "Structure of MgCl_2.RbCl.6H_2O." Acta.Crystallogr.C47. 251-254 (1991)
[Publications] N.Fukushima: "Dissolution of Alkali Fluoride and Chloride Crystals in Water Studied by Molecular Dynamics Simulations." Z.Naturforsch. 46a. 193-202 (1991)
[Publications] K.Waizumi: "X‐ray Diffraction Studies on Ternary MgCl_2‐KCl‐H_2O and MgCl_2‐CsCl‐H_2O Solutions Saturated with the Corresponding Double Salts." Z.Naturforsch. 46a. 307-312 (1991)
[Publications] H.Wakita: "Structure Determination of Zinc lodide Complexes Formed in Aqueous Solutions." J.Solution Chem.20. 643-668 (1991)
[Publications] G.Johansson: "Coordination around Thorium(IV)in Aqueous Perchlorate,Chloride and Nitrate Solutions." J.Solution Chrm.20. 775-792 (1991)
[Publications] G.Johansson: "Structure of the Solvated Metal lons in Nitrate and Chloride Solutions of Erbium(III)and Yttrium(III)in Dimethyl Sulfoxide." J.Solution Chem.20. 859-874 (1991)
[Publications] K.Waizumi: "Crystallographic Investigations on [Mg(H_2O)_6]XCl_3 Double Salts(X^+=K^+,Rb^+,Cs^+,NH_4^+):Crystal Structure of [Mg(H_2O)_6]CaCl_3." Amer.Mineralogist. 76. 1884-1888 (1991)
[Publications] H.Ohtaki: "Nucleation Processes of NaCl and CsF Crystals from Aqueous Solutions Studied by Molecular Dynamics Simulations." Pure & Appl.Chem.63. 1743-1748 (1991)
[Publications] H.Suzuki: "Structures of Zinc(II)and Copper(II)Chloride N,N‐Dimethylformamide Solvates" Acta Crystallogr.C47. 1838-1842 (1991)
[Publications] Y.Tamura: "An MD Simulation of Concented Aqueous Solutions of Caesium Iodide." Z.Naturforsch.46a. (1991)
[Publications] H.Ohtaki: "A Structural Study on Saturated Aqueous Solutions of Some Alkali Halides‐by X‐Ray Diffraction." J.Solution Chem.210. (1992)
[Publications] H.Ohtaki: "An Attempt to Parameterize the Structuredness of Solvates." J.Solution Chem.21. (1992)
[Publications] K.Waizumi: "X‐ray Strucrural Studies on FeBr_2・4H_2O,CoBr_2・4H_2O,NiCl_2・4H_2O,CuBr_2・4H_2O.Cis/trans Selectivity in Transition Metal(II)Dihalide Tetrahydrates." Inoeg.Chim.Acta.
[Publications] H.Ohtaki: "Structure of Divalent Transition‐Metal Complexes at Consecutive Steps of Interaction with Halide and Thiocyanate lons in Solution." J.Indian Chem.Soc.
[Publications] K.Waizumi: "Structure of 2RbCl.CuCl_2.2H_2O." Acta Crystallogr.
[Publications] T.Yamaguchi: "Pulsed Neutron Diffraction Studies on Lanthanide(III)Hydration in Aqueous Perchlorate Solutions." Z.Naturforsh.46a. 84-88 (1991)
[Publications] K.Ichikawa: "Neutron‐diffraction Investigation of the Intramolecular Structures of a Water Molecule in the Liquid State at High Temperatures." Mol.Phys.73. 79-86 (1991)
[Publications] T.Takamuku: "X‐ray Diffraction and Raman Spectroscopic Studies on Supercooled and Glassy Aqueous Zinc(II)lodide Solutions." J.Phys.Chem.95. 10098-10103 (1991)
[Publications] K.Oki: "Intermediate Valences of Ce and Electrical Resistivity Chenges of Pd‐Ce Intermetallic Compunds." J.Appl.Phys.69. 4693-4695 (1991)
[Publications] T.Takamuku: "Raman Spectroscopic and X‐ray Diffraction Studies on Concentrated Aqueous Zinc(II)Bromide Solutions at High Temperatures." Z.Naturforsch.47a. (1992)
[Publications] K.Nakata: "Kinetic Studies on the Teminal Ligand Substitution Reactions of Acetate‐Bridged Trinuclear Molybdenum and Tungsten Cluster Complexes,[Mo_3(μ_3‐CCH_3)(μ3‐O)(μ‐CH_3COO)_6(L)_3(L=H_2O or Pyridine)and [W_3(μ_3‐O)(μ‐CH_3COO)_6(H_2O_3]^<2+>." Inorg.Chem.30. 1575-1579 (1991)
[Publications] Y.Sasaki: "Circular Dichroism Spectrophotometric Study of [Mo_2(μ‐O)_2(O)_2(R‐cysteinato)2]^<2-> in Aqueous Micellar Solutions." Inorg.Chem.Acta.183. 15-19 (1991)
[Publications] 佐々木陽一: "金属クラスタ-錯体の原子価状態と構造および反応性。" 表面. 29. 220-230 (1991)
[Publications] H.Kato: "Preparation and Properties of Oxo‐centered Trinuclear Chromium(III)Complexes with Bridging Optically Active Amino Acids,[Cr(μ_3‐O)(μ‐O,O'‐amino‐acid)_6(H_2O)_3]^<7+>." Bull.Chem.Soc.Jpn.64. 3463-3465 (1991)
[Publications] T.Ochi: "Rapid Unidentate‐Chelate Equilibrium of Acetate Ligands on the Ruthenium‐Analog of the Hemerythrin Active Center and Crystal Structure of [Ru_2(μ‐CH_3COO)_2(μ‐O)(CH_3COO)_2(H_2O)(CH_3OH)(P(C_6H_5)_3)_2]・having Unidentate Acetates" Chem.Lett.2019-2022 (1991)
[Publications] Y.Sasaki: "Prepation,Structure and Properties of the Bis(μ‐acetato)(μ‐oxo)Ruthenium(III)Dimer,[Ru_2(μ‐CH_3COO)_2(μ‐O)(pridine)_6]^<2+>and [Ru_2(μ‐CH_3COO)_2(μ‐O)(2,2'‐bipyridine)_2(pridine)_2]^<2+>." Inorg.Chem.30. 4903-4908 (1991)
[Publications] H.Kobayashi: "Magnetic Properties of Oxygen Centered Trinuclear Ru(III)and Rh(III)Complexes." Bull.Chem.Soc.Jpn.65. 198-202 (1992)
[Publications] D.Akashi: "Preparation and Electro‐chemical Response of Poly (4‐vinylpyridine)‐Coordinated Oxo‐Acetate Triruthenium Cluster Film." Chem.Lett.143-146 (1992)
[Publications] H.Ohtaki: "Local Structure of Macromolecule‐Metal Complexes in Solutions,in"Macromolecular Complexes"." VCH,New York, 35 (1991)
[Publications] 大瀧仁志: "食塩結晶の溶解と核生成を視る。" 数理科学, 5 (1991)
[Publications] 大瀧仁志: "化学の本を考える。" 化学, 7 (1991)
[Publications] 脇田久伸: "水の構造と物性。" 繊維と工業,
[Publications] 舟橋重信: "溶液内反応。" ぶんせき, 2 (1991)
[Publications] 石原浩二: "溶液内迅速反応の測定と解折。" ぶんせき, 9 (1991)

1991 Fiscal Year Annual Research Report

溶液の非平衡過程の分子論的アプロ-チ・反応活性種の構造

Principal Investigator

大瀧 仁志 岡崎国立共同研究機構, 分子科学研究所, 教授 (80022549)

Research Products

[Publications] K.Waizumi: "Structure of MgCl_2.RbCl.6H_2O." Acta.Crystallogr.C47. 251-254 (1991)

[Publications] N.Fukushima: "Dissolution of Alkali Fluoride and Chloride Crystals in Water Studied by Molecular Dynamics Simulations." Z.Naturforsch. 46a. 193-202 (1991)

[Publications] K.Waizumi: "X‐ray Diffraction Studies on Ternary MgCl_2‐KCl‐H_2O and MgCl_2‐CsCl‐H_2O Solutions Saturated with the Corresponding Double Salts." Z.Naturforsch. 46a. 307-312 (1991)

[Publications] H.Wakita: "Structure Determination of Zinc lodide Complexes Formed in Aqueous Solutions." J.Solution Chem.20. 643-668 (1991)

[Publications] G.Johansson: "Coordination around Thorium(IV)in Aqueous Perchlorate,Chloride and Nitrate Solutions." J.Solution Chrm.20. 775-792 (1991)

[Publications] G.Johansson: "Structure of the Solvated Metal lons in Nitrate and Chloride Solutions of Erbium(III)and Yttrium(III)in Dimethyl Sulfoxide." J.Solution Chem.20. 859-874 (1991)

[Publications] K.Waizumi: "Crystallographic Investigations on [Mg(H_2O)_6]XCl_3 Double Salts(X^+=K^+,Rb^+,Cs^+,NH_4^+):Crystal Structure of [Mg(H_2O)_6]CaCl_3." Amer.Mineralogist. 76. 1884-1888 (1991)

[Publications] H.Ohtaki: "Nucleation Processes of NaCl and CsF Crystals from Aqueous Solutions Studied by Molecular Dynamics Simulations." Pure & Appl.Chem.63. 1743-1748 (1991)

[Publications] H.Suzuki: "Structures of Zinc(II)and Copper(II)Chloride N,N‐Dimethylformamide Solvates" Acta Crystallogr.C47. 1838-1842 (1991)

[Publications] Y.Tamura: "An MD Simulation of Concented Aqueous Solutions of Caesium Iodide." Z.Naturforsch.46a. (1991)

[Publications] H.Ohtaki: "A Structural Study on Saturated Aqueous Solutions of Some Alkali Halides‐by X‐Ray Diffraction." J.Solution Chem.210. (1992)

[Publications] H.Ohtaki: "An Attempt to Parameterize the Structuredness of Solvates." J.Solution Chem.21. (1992)

[Publications] K.Waizumi: "X‐ray Strucrural Studies on FeBr_2・4H_2O,CoBr_2・4H_2O,NiCl_2・4H_2O,CuBr_2・4H_2O.Cis/trans Selectivity in Transition Metal(II)Dihalide Tetrahydrates." Inoeg.Chim.Acta.

[Publications] H.Ohtaki: "Structure of Divalent Transition‐Metal Complexes at Consecutive Steps of Interaction with Halide and Thiocyanate lons in Solution." J.Indian Chem.Soc.

[Publications] K.Waizumi: "Structure of 2RbCl.CuCl_2.2H_2O." Acta Crystallogr.

[Publications] T.Yamaguchi: "Pulsed Neutron Diffraction Studies on Lanthanide(III)Hydration in Aqueous Perchlorate Solutions." Z.Naturforsh.46a. 84-88 (1991)

[Publications] K.Ichikawa: "Neutron‐diffraction Investigation of the Intramolecular Structures of a Water Molecule in the Liquid State at High Temperatures." Mol.Phys.73. 79-86 (1991)

[Publications] T.Takamuku: "X‐ray Diffraction and Raman Spectroscopic Studies on Supercooled and Glassy Aqueous Zinc(II)lodide Solutions." J.Phys.Chem.95. 10098-10103 (1991)

[Publications] K.Oki: "Intermediate Valences of Ce and Electrical Resistivity Chenges of Pd‐Ce Intermetallic Compunds." J.Appl.Phys.69. 4693-4695 (1991)

[Publications] T.Takamuku: "Raman Spectroscopic and X‐ray Diffraction Studies on Concentrated Aqueous Zinc(II)Bromide Solutions at High Temperatures." Z.Naturforsch.47a. (1992)

[Publications] Y.Sasaki: "Circular Dichroism Spectrophotometric Study of [Mo_2(μ‐O)_2(O)_2(R‐cysteinato)2]^<2-> in Aqueous Micellar Solutions." Inorg.Chem.Acta.183. 15-19 (1991)

[Publications] 佐々木 陽一: "金属クラスタ-錯体の原子価状態と構造および反応性。" 表面. 29. 220-230 (1991)

[Publications] H.Kato: "Preparation and Properties of Oxo‐centered Trinuclear Chromium(III)Complexes with Bridging Optically Active Amino Acids,[Cr(μ_3‐O)(μ‐O,O'‐amino‐acid)_6(H_2O)_3]^<7+>." Bull.Chem.Soc.Jpn.64. 3463-3465 (1991)

[Publications] T.Ochi: "Rapid Unidentate‐Chelate Equilibrium of Acetate Ligands on the Ruthenium‐Analog of the Hemerythrin Active Center and Crystal Structure of [Ru_2(μ‐CH_3COO)_2(μ‐O)(CH_3COO)_2(H_2O)(CH_3OH)(P(C_6H_5)_3)_2]・having Unidentate Acetates" Chem.Lett.2019-2022 (1991)

[Publications] Y.Sasaki: "Prepation,Structure and Properties of the Bis(μ‐acetato)(μ‐oxo)Ruthenium(III)Dimer,[Ru_2(μ‐CH_3COO)_2(μ‐O)(pridine)_6]^<2+>and [Ru_2(μ‐CH_3COO)_2(μ‐O)(2,2'‐bipyridine)_2(pridine)_2]^<2+>." Inorg.Chem.30. 4903-4908 (1991)

[Publications] H.Kobayashi: "Magnetic Properties of Oxygen Centered Trinuclear Ru(III)and Rh(III)Complexes." Bull.Chem.Soc.Jpn.65. 198-202 (1992)

[Publications] D.Akashi: "Preparation and Electro‐chemical Response of Poly (4‐vinylpyridine)‐Coordinated Oxo‐Acetate Triruthenium Cluster Film." Chem.Lett.143-146 (1992)

[Publications] H.Ohtaki: "Local Structure of Macromolecule‐Metal Complexes in Solutions,in"Macromolecular Complexes"." VCH,New York, 35 (1991)

[Publications] 大瀧 仁志: "食塩結晶の溶解と核生成を視る。" 数理科学, 5 (1991)

[Publications] 大瀧 仁志: "化学の本を考える。" 化学, 7 (1991)

[Publications] 脇田 久伸: "水の構造と物性。" 繊維と工業,

[Publications] 舟橋 重信: "溶液内反応。" ぶんせき, 2 (1991)

[Publications] 石原 浩二: "溶液内迅速反応の測定と解折。" ぶんせき, 9 (1991)

大瀧仁志岡崎国立共同研究機構, 分子科学研究所, 教授 (80022549)

[Publications] 佐々木陽一: "金属クラスタ-錯体の原子価状態と構造および反応性。" 表面. 29. 220-230 (1991)

[Publications] 大瀧仁志: "食塩結晶の溶解と核生成を視る。" 数理科学, 5 (1991)

[Publications] 大瀧仁志: "化学の本を考える。" 化学, 7 (1991)

[Publications] 脇田久伸: "水の構造と物性。" 繊維と工業,

[Publications] 舟橋重信: "溶液内反応。" ぶんせき, 2 (1991)

[Publications] 石原浩二: "溶液内迅速反応の測定と解折。" ぶんせき, 9 (1991)