1990 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	02245106
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)	佐々木陽一東北大学, 理学部, 助教授 (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	本研究班は4名の中核となる計画研究班員と7組の公募研究班とから成っている。中核となる計画班員は、溶液内反応において生成する反応活性種あるいは反応中間体の分子構造を決定することに目的を集中し、今年度はさまざまな研究を展開した。大瀧は班全体を総括するとともに、舟橋の協力を得て、反応中間体の構造を決定するため、ストップド・フロ-法とEXAFS法とを組み合わせた迅速EXAFS測定装置の建設に努力した。現在装置の試運転を行っており、平成3年度には新しい成果が挙げられることを期待している。舟橋は迅速EXAFS測定装置の設置に協力するとともに、吸収スペクトルの測定から溶液内反応を研究するために、従来用いられていた2液混合セルをさらに改良し、3液が混合できる装置の開発につとめた。この装置により、今後3成分系の反応中間体の構造や組成が決定されるものと期待されている。山口はイメ-ジング・プレ-トを用いて溶液X線回折測定がさらに短時間で且つ精度よく測定できるように工夫し、電解質水溶液の過冷却状態あるいはガラス状態での構造を決定しようと試みた。さらにこの方法を結晶の時間分解構造測定に適用することを考えており、平成3年度以降、この方法による新しい成果が得られるものと思われる。佐々木はルテニウム(III)とクロム(III)イオンを含む三核錯体を合成したが、その反応中間体としてルテニウム(III)イオン2個を含む錯体が生成することを見出し、その構造をわれわれが開発している迅速EXAFS法などを用いて決定しようと試みている。これらの研究は公募班員とも密接に連けいを保ちながら行われており、すでにいくつかの新しい共同研究計画が進行している。このように本年度の研究計画はほぼ当初の計画にしたがい、順調に展開していると考えている。

Research Products

(32 results)

All Other

All Publications (32 results)

[Publications] H.Otaki: "The Structure of Nickel(II) and Copper (II) Complexes with 1,4,8,11ーTetraazaーcyclotetradecane in Aqueous Solution as Studied by the XーRay Diffraction Method." J.Macromol.Sci.Chem.
[Publications] K.Waizumi: "Structure of MgCl_2RbCl_6H_2O." Acta Crystallogr.
[Publications] H.Wakita: "Structure Determination of Zinc Iodide Complexes Formed in Aqueous Solution." J.Solution.Chem.
[Publications] K.Waizumi: "Crystallographic Investigations on [Mg(H_2O)_6]BCl_3 Couble Salts (B^+=K^+,Rb^+,Cs^+,NH_4^+).Crystal Structure of [Mg(H_2O)_6]CsCl_3." Amer.Mineralogist.
[Publications] N.Fukushima: "Dissolution of Alkali Fluoride and Chloride Crystals in Water Studied by Molecular Dynamics Simulations." Z.Naturforsch.
[Publications] G.Johansson: "Coordination around Thorium(IV) in Aqueous Perchlorate,Chloride and Nitrate Solutions." J.Solution Chem.
[Publications] H.Abe: "Characterization of Highly Selective CuーNi Amination Catalysts." Chem.Lett.401-404 (1990)
[Publications] A.Rajalakshmi: "Structural Studies on Superionic Glass AglーAg_2 OーMoO_3" J.Phys.Soc.Jpn.59. 1252-1263 (1990)
[Publications] H.Suzuki: "Formation of Chloro Complexes of Manganese(II),Cobalt(II),Nickel(II) and Zinc(II) in Dimethyl Sulfoxide." J.Chem.Soc.Faraday Trans.86. 2179-2185 (1990)
[Publications] T.Radnai: "An Xーray Diffraction Study on Zn(II) Complexes with αーAlaninate lon in Aqueous Solution." Bull.Chem.Soc.Jpn.63. 3420-3425 (1990)
[Publications] K.Waizumi: "In Situ Observation of the Phase Transition among Cobalt(II) Dichloride Hydrates and Crystal Structures of the Tetraー and Hexahydrates." Bull.Chem.Soc.Jpn.63. 3426-3433 (1990)
[Publications] K.Waizumi: "Xーray Diffraction Studies on Ternary MgCl_2ーKClーH_2O and MgCl_2ーCsClーH_2O Solutions Saturated with the Corresponding Double Salts." Z.Naturforsch.
[Publications] H.Otaki: "Structure of Divalent transitionーMetal Complexes at Consecutive Steps of Interaction with Halide and Thiocyanate Ions in Solution." Indian J.Chem.
[Publications] H.Suzuki: "Structures of Zinc(II) and Copper(II) Chloride N,NーDimethylformamide Solvates" Acta Crystallogr.,Sect.C.
[Publications] G.Johansson: "Structure of the Solvated Metal Ions in Nitrate and Chloride Solutions of Erbium(II) and Yttrium(II)in Dimethyl Sulfoxide(DMSO)." J.Solution Chem.
[Publications] M.Inamo: "Variable Pressure Kinetic and Equilibrium Study of the Complexation of the Beryllium(II) Ion with 4ーIsopropyltropolone in Acidic Aqueous Solution." Inorg.Chem.
[Publications] K.Ishihara: "Mechanistic Study of the Complex Formation of Boric Acid." Inorg.Chem.(Sー1).
[Publications] T.Tanaka: "Kinetic Studies on Conformational Change of Cryptand(221) and Formation of Copper(U) Cryptate(221) in Dimethyl Sulfoxide,N,NーDimethylformamide,and Acetonitrile." J.Amer.Chem.Soc.
[Publications] M.Kodama: "Calorimetric Investigations of the Stability of Octadecyltrimethylammonium HalideーWater System." J.Phys.Chem.94. 815-819 (1990)
[Publications] M.Kodama: "Thermal Characterization of the Mode of Phase Transition in the Dioctadecyldimethylammonium BromideーWater System in Relation to the Stability of Its Gel Phase." J.Phys.Chem.94. 1550-1554 (1990)
[Publications] T.Takamuku: "Structure of Highly Concentrated Aqueous Zinc(II) Iodide Solutions in Supercooled and Glassy States." J.Phys.Chem.
[Publications] T.Yamaguchi: "Pulsed Neutron Diffraction Studies on Lanthanide(III) Hydration in Aqueous Perchlorate Solutions." Z.Naturforsch.
[Publications] T.Yamaguchi: "Diffraction and XーRay Absorption Studies of Electrolyte Solutions." Pure & Appl.Chem.62. 2251-2258 (1990)
[Publications] Y.Sasaki: "Structure and Properties of the Bis(μーacetato)(μーoxo)ーRuthenium(III) Dimers,[Ru_2(μーCH_3COO)_2(μーO)(pyridine)_6]^<2+> and [Ru_2(μーCH_3COO)_2(μーO)(2,2'ーbipyridine)_2(pyridine)_6]^<2+>" Inorg.Chem.
[Publications] Y.Sasaki: "Circular Dichroism Spectrophotometric Study of [Mo_2(μーO)ー(O)_2(Rーcysteinato)_2]^<2ー> in Aqueous Solutions." Inorg.Chim.Acta.
[Publications] K.Nakata: "Kinetic Studies on the Terminal Ligand Substitution Reactions of AcetateーBridged Trinuclear Molybdenum and Tungsten Cluster Complexes,[Mo_3(μ_3ーCCH_3)(μ_3ーO)(μーCH_3COO)_6(L)_3]^+ (L=H_2O or pyridine) and [W_3(μ_3ーO)(μーCH_3COO)_6(H_2O)_3]^<2+>." Inorg.Chem.
[Publications] T.Yamaguchi: "Unusual C,OーBridging Coordination of Acetate and Acetylacetone Ligands in the Platinum Clusters,[PtIII_2(μーCH_3COOーC,O)_2(μーCH_3COOーO,O')_2Cl_2]^<2ー> and [Pt^<II>_4(μーCH_3COOーO,O')_4(μーCH_3COCH_3ーO,C^3)_4]." J.Am.Chem.Soc.112. 4038-4040 (1990)
[Publications] J.F.Ojo: "Kinetics of the OuterーSphere Oxidation of the Mixed Molybdenum(V)ーTungsten(V) Dinuclear Complex,[MoW(O)_2(μーO)_2(μーedtaーN,N')]^<2ー> and of the MixedーBridged Complex [W_2(O)_2(μーO)(μーS)(μーedtaーN,N')]^<2ー> by [Ir^<IV>Cl_6]^<2ー> in Aqueous Solution." Inorg.Chem.29. 1712-1716 (1990)
[Publications] 大瀧仁志: "イオンの水和" 共立出版, 104 (1990)
[Publications] 大瀧仁志: "数理科学食品結晶の溶解と核形成を視る" (株)サイエンス, 6
[Publications] 大瀧仁志: "電気化学および工業物理化学電解質溶液の構造と反応" 電気化学協会, 8 (1990)
[Publications] 大瀧仁志: "ニュ-セラミックス水に溶けるとはー溶液の構造とダイナミックスー" ニュ-セラミックス談話会, 5 (1990)

1990 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] H.Otaki: "The Structure of Nickel(II) and Copper (II) Complexes with 1,4,8,11ーTetraazaーcyclotetradecane in Aqueous Solution as Studied by the XーRay Diffraction Method." J.Macromol.Sci.Chem.

[Publications] K.Waizumi: "Structure of MgCl_2RbCl_6H_2O." Acta Crystallogr.

[Publications] H.Wakita: "Structure Determination of Zinc Iodide Complexes Formed in Aqueous Solution." J.Solution.Chem.

[Publications] K.Waizumi: "Crystallographic Investigations on [Mg(H_2O)_6]BCl_3 Couble Salts (B^+=K^+,Rb^+,Cs^+,NH_4^+).Crystal Structure of [Mg(H_2O)_6]CsCl_3." Amer.Mineralogist.

[Publications] N.Fukushima: "Dissolution of Alkali Fluoride and Chloride Crystals in Water Studied by Molecular Dynamics Simulations." Z.Naturforsch.

[Publications] G.Johansson: "Coordination around Thorium(IV) in Aqueous Perchlorate,Chloride and Nitrate Solutions." J.Solution Chem.

[Publications] H.Abe: "Characterization of Highly Selective CuーNi Amination Catalysts." Chem.Lett.401-404 (1990)

[Publications] A.Rajalakshmi: "Structural Studies on Superionic Glass AglーAg_2 OーMoO_3" J.Phys.Soc.Jpn.59. 1252-1263 (1990)

[Publications] H.Suzuki: "Formation of Chloro Complexes of Manganese(II),Cobalt(II),Nickel(II) and Zinc(II) in Dimethyl Sulfoxide." J.Chem.Soc.Faraday Trans.86. 2179-2185 (1990)

[Publications] T.Radnai: "An Xーray Diffraction Study on Zn(II) Complexes with αーAlaninate lon in Aqueous Solution." Bull.Chem.Soc.Jpn.63. 3420-3425 (1990)

[Publications] K.Waizumi: "In Situ Observation of the Phase Transition among Cobalt(II) Dichloride Hydrates and Crystal Structures of the Tetraー and Hexahydrates." Bull.Chem.Soc.Jpn.63. 3426-3433 (1990)

[Publications] K.Waizumi: "Xーray Diffraction Studies on Ternary MgCl_2ーKClーH_2O and MgCl_2ーCsClーH_2O Solutions Saturated with the Corresponding Double Salts." Z.Naturforsch.

[Publications] H.Otaki: "Structure of Divalent transitionーMetal Complexes at Consecutive Steps of Interaction with Halide and Thiocyanate Ions in Solution." Indian J.Chem.

[Publications] H.Suzuki: "Structures of Zinc(II) and Copper(II) Chloride N,NーDimethylformamide Solvates" Acta Crystallogr.,Sect.C.

[Publications] G.Johansson: "Structure of the Solvated Metal Ions in Nitrate and Chloride Solutions of Erbium(II) and Yttrium(II)in Dimethyl Sulfoxide(DMSO)." J.Solution Chem.

[Publications] M.Inamo: "Variable Pressure Kinetic and Equilibrium Study of the Complexation of the Beryllium(II) Ion with 4ーIsopropyltropolone in Acidic Aqueous Solution." Inorg.Chem.

[Publications] K.Ishihara: "Mechanistic Study of the Complex Formation of Boric Acid." Inorg.Chem.(Sー1).

[Publications] T.Tanaka: "Kinetic Studies on Conformational Change of Cryptand(221) and Formation of Copper(U) Cryptate(221) in Dimethyl Sulfoxide,N,NーDimethylformamide,and Acetonitrile." J.Amer.Chem.Soc.

[Publications] M.Kodama: "Calorimetric Investigations of the Stability of Octadecyltrimethylammonium HalideーWater System." J.Phys.Chem.94. 815-819 (1990)

[Publications] M.Kodama: "Thermal Characterization of the Mode of Phase Transition in the Dioctadecyldimethylammonium BromideーWater System in Relation to the Stability of Its Gel Phase." J.Phys.Chem.94. 1550-1554 (1990)

[Publications] T.Takamuku: "Structure of Highly Concentrated Aqueous Zinc(II) Iodide Solutions in Supercooled and Glassy States." J.Phys.Chem.

[Publications] T.Yamaguchi: "Pulsed Neutron Diffraction Studies on Lanthanide(III) Hydration in Aqueous Perchlorate Solutions." Z.Naturforsch.

[Publications] T.Yamaguchi: "Diffraction and XーRay Absorption Studies of Electrolyte Solutions." Pure & Appl.Chem.62. 2251-2258 (1990)

[Publications] Y.Sasaki: "Structure and Properties of the Bis(μーacetato)(μーoxo)ーRuthenium(III) Dimers,[Ru_2(μーCH_3COO)_2(μーO)(pyridine)_6]^<2+> and [Ru_2(μーCH_3COO)_2(μーO)(2,2'ーbipyridine)_2(pyridine)_6]^<2+>" Inorg.Chem.

[Publications] Y.Sasaki: "Circular Dichroism Spectrophotometric Study of [Mo_2(μーO)ー(O)_2(Rーcysteinato)_2]^<2ー> in Aqueous Solutions." Inorg.Chim.Acta.

[Publications] K.Nakata: "Kinetic Studies on the Terminal Ligand Substitution Reactions of AcetateーBridged Trinuclear Molybdenum and Tungsten Cluster Complexes,[Mo_3(μ_3ーCCH_3)(μ_3ーO)(μーCH_3COO)_6(L)_3]^+ (L=H_2O or pyridine) and [W_3(μ_3ーO)(μーCH_3COO)_6(H_2O)_3]^<2+>." Inorg.Chem.

[Publications] T.Yamaguchi: "Unusual C,OーBridging Coordination of Acetate and Acetylacetone Ligands in the Platinum Clusters,[PtIII_2(μーCH_3COOーC,O)_2(μーCH_3COOーO,O')_2Cl_2]^<2ー> and [Pt^<II>_4(μーCH_3COOーO,O')_4(μーCH_3COCH_3ーO,C^3)_4]." J.Am.Chem.Soc.112. 4038-4040 (1990)

[Publications] 大瀧 仁志: "イオンの水和" 共立出版, 104 (1990)

[Publications] 大瀧 仁志: "数理科学 食品結晶の溶解と核形成を視る" (株)サイエンス, 6

[Publications] 大瀧 仁志: "電気化学および工業物理化学 電解質溶液の構造と反応" 電気化学協会, 8 (1990)

[Publications] 大瀧 仁志: "ニュ-セラミックス 水に溶けるとはー溶液の構造とダイナミックスー" ニュ-セラミックス談話会, 5 (1990)

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] 大瀧仁志: "イオンの水和" 共立出版, 104 (1990)

[Publications] 大瀧仁志: "数理科学食品結晶の溶解と核形成を視る" (株)サイエンス, 6

[Publications] 大瀧仁志: "電気化学および工業物理化学電解質溶液の構造と反応" 電気化学協会, 8 (1990)

[Publications] 大瀧仁志: "ニュ-セラミックス水に溶けるとはー溶液の構造とダイナミックスー" ニュ-セラミックス談話会, 5 (1990)