1992 Fiscal Year Annual Research Report

溶液の非平衝過程の分子論的アプローチ・反応活性種の構造

Research Project

Project/Area Number	04215105
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)	大野弘幸東京農工大学, 工学部, 助教授 (00176968) 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	反応活性種の構造 / 迅速EXAFS / 高圧ストップト・フローNMR / エチレンジアミン溶媒交換反応 / 金属クラスター錯体 / 迅速時間合解X線回折 / 結晶成長の動的過程 / 溶解過程
Research Abstract	本研究では、計画班員5名が分担・協力して反応活性種の構造に関して研究するとともに、公募班員とも積極的に協同研究を展開し、数々の大きな成果を得た。以下に主な成果を要約する。1.大瀧・舟橋は、実験室スケールのエネルギー分散型迅速EXAFS測定装置を開発し、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ていたヘテロ二核中間体の構造を直接決定することに成功した。2.舟橋は世界で初の高圧ストップト・フローNMR測定装置の開発に成功し、高圧下で種々の溶媒交換反応や錯形成反応を追跡し、圧力効果から遷移状態の構造を推定した。たとえば、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、金属(II)イオンのエチレンジアミン溶媒交換反応では、エチレンジアミンが単座で配位した中間体が存在することを示した。3.山口はイメージング・プレート検出器を用いた迅速時間分解X線回折装置の開発に成功した。結晶成長の動的過程を解明するため、室温から過冷却状態にいたる溶液中のイオンや水分子の静的・動的構造をラマン分光法、X線・中性子回折法等により種々の反応過程について研究した。たとえば、ジおよびトリプロモ亜鉛(II)錯体の第一配位圏から解離した溶媒分子が水素結合により系内で安定化するため、低温でテトラプロモ亜鉛(II)錯体の生成が有利になることを示した。4.佐々木は複雑な金属クラスター錯体の生成や電子移動過程中に存在する中間体の役割を解明するため、オキソ-アセタト袈橋型のルテニウムクラスター錯体を対象として合成的研究を遂行し、種々の反応中間体の構造に関する知見を得た。そして個々の知見を再構築することによって、錯体の系統的合成経路を明らかにした。5.大野は高分子溶液中における各種無機塩の溶解過程を解明した。大瀧は本研究の目的に沿った総括を行い、本研究は、当初の計画通り遂行できた。

Research Products

(38 results)

All Other

All Publications (38 results)

[Publications] H.Ohtaki: "A Structural Study of Saturated Aqueous Solutions of Some Alkali Halides by X-Ray Diffraction" J.Solution Chem.21. 23-38 (1992)
[Publications] H.Ohtaki: "An Attempt to Parameterize the Structuredness of Solvents" J.Solution Chem.21. 39-47 (1992)
[Publications] K.Waizumi: "Structure of 2RbCl・CuClX_2・2HX_2O." Acta Crystallogr.C48. 1374-1376 (1992)
[Publications] K.Waizumi: "X-Ray Structural Studies of FebrX_2・4HX_2O,CoBrX_2O,NiClX_2D2・4HX_2O,and CuBrX_2・4HX_2O. Cis/trans Silictivity in Transition Metal(II)Dihalide Tetrahydrate." Inorg.Chim.Acta. 192. 173-181 (1992)
[Publications] T.Radnai: "X-Ray Diffraction Studies on the Structure of the Tri- and Tetrathiocyanatomanganate(II) Complexes and Solvated Lithium Ion in N,N-Dimethylformamide." Bull.Chem.Soc.Jpn.65. 1445-1452 (1992)
[Publications] K.Ozutsumi: "EXAFS and X-Ray Diffraction Studies on the Structure of the Tetrathiocyanatocadmate(II) Complex in Dimethyl Sulfoxide." Bull.Chem.Soc.Jpn.65. 2104-2113 (1992)
[Publications] K.Waizumi: "Density Function Calculations on the Geometries and Dissociation Energies of [M(HX_2O)X_6]X^<2+> Ions MX^<2+>=CrX^<2+>,MnX^<2+>,FeX^<2+>,CoX^<2+>,NiX^<2+>,CuX^<2+>,and ZnX^<2+>." Chem.Lett.1489-1492 (1992)
[Publications] T.Radnai: "Intramolecular and Liquid Structures of Tetramethylurea Studied by Means of X-Ray Diffraction." Z.Naturforsch.47a. 1003-1010 (1992)
[Publications] H.Ohtaki: "Dissolution and Nucleation Phenomena of Salts in Water.Molecular Dynamic Approaches and Supporting Solution X-Ray Diffraction Measurements." Pure&Appl.Chem.65. 203-211 (1993)
[Publications] S.Patnaik: "A Structural Study on AgI-AgX_2O-CrOX_3 Glass." J.Phys.Soc.Jpn.62. 536-543 (1993)
[Publications] S.Patnaik: "An X-Ray RDF Study of the Glass 30AgI-45AgX_2O-25 VX_2OX_5.Solid State Ionics." Solid State Ionics.
[Publications] H.Ohtaki: "Structure and Dynamics of Hydrated Ions." Chem.Rev.
[Publications] H.Ohtaki: "Molecular Aspects on the Dissolution and Nucleation of Ionic Crystals in Water." Adv.Inorg.Chem.
[Publications] H.Ohtaki: "Structure of Divalent Metal Complexes with Halide and Thiocyanate Ions in Solution." J.Indian Chem.Soc.
[Publications] Y.Shimizu: "Kinetic Studies of the Incorporation of the Zinc(II) Ioninto water-Soluble N-Phenyl-Substituted Porphyrins.Deformation Effect on the Metallation Rate." Bull.Chem.Soc.Jpn.65. 771-776 (1992)
[Publications] S.Soyama: "Variable-Temperature and -Pressure Multinuclear Magnetic Resonance Study on Solvent Exchange at Tris(ethylenediamine)nickel(II) Ione in Ethylenediamine." Inorg.Chem.31. 536-538 (1992)
[Publications] S.Funahashi: "High-Pressure Stopped-Flow Nuclear Magnetic Resonance Apparatus for the Study of Fast Reaction in Solution." Rev.Sci.Instrum.
[Publications] S.Aizawa: "Synthesis,Structural Characterization,and Metallation of N-o-Tolyl-5,10,15,20-tetraphenylporphine:Deformation Effect due to a Bulky N-Substituent Group." Inorg.Chem.
[Publications] S.Yamashita: "A New Laboratory XAFS Spectrometer for X-Ray Absorption Spectra of Light Elements." X-Ray Spectrometry. 21. 91-97 (1992)
[Publications] T.Takamuku: "Raman Spectroscopic and X-ray Diffraction Studies on Concentrated Aqueous Zinc(II) Bromide Solution at High Temperatures." Z.Naturforsch. 47a. 485-492 (1992)
[Publications] T.Takamuku: "Structure of Supercooled Aqueous Zinc(II) Bromide Solutions by Raman X-ray Scattering Methode." Z.Naturforsch. 47a. 841-848 (1992)
[Publications] T.Takamuku: "NMR Study on Dynamics of Water Molecules in Concentrated Aqueous Zinc(II) Bromide Solutions at Various Temteratures." J.Phys.Chem.96. 9487-9492 (1992)
[Publications] T.Kurisaki: "Temperature Effecrt on the Structure of Hydrated Lanthanide(II) Ions in Crystales and Solution." J.Alloys and Compounds.
[Publications] Y.Yamasaki: "Determination of the Absolute Configuration of Sodium(-)X_<589>-Bis(N-methyliminodiacetato)cobalt(III) Trihydrate." Acta Crystallogr.
[Publications] H.Wakita: "A XANES Study of Square Copper(II) Complexes." Advances in X-Ray Analysis. 35. 1115-1120 (1992)
[Publications] T.Yamaguchi: "Study on Stepwise Copper(II) Chloride Complexes in Acetonitrile by Fluorescence XAFS Spectroscopy Using Thermodynamic Data." Jap.J.Appl.Phys.
[Publications] T.Yamaguchi: "X-Ray Absorption Study on Aqueous Ionic Solutions in the Liquid and Glassy States." Jap.J.Appl.Phys.
[Publications] T.Yamaguchi: "XAFS Study with an In Situ Electrochemical Cell on Manganese Schiff Base Complexes as a Model of Photosystem II." Jap.J.Appl.Phys.
[Publications] H.Miki: "Phosphorescence from the Triplet Spin Sublevels of Hexanuclear Molybdemum(II) Chloride Cluster Ion,[MoX_6ClX_<14>]X^<2->.Relative Radiative Rate Constants for Emitting Sublevels." J.Phys.Chem.96. 3236-3239 (1992)
[Publications] M.Ebihara: "Syntheses,Structures and Properties of Pxidized Hexamolybdenum Clusters [(MoX_6XX_7Y)X'X_6]X^<2->(X=X'=Cl,Br;Y=S,Se)." Inorg.Chem.31. 1644-1649 (1992)
[Publications] M.Abe: "Kinetic Studies on the Terminal Phyridine Exchange Reaction of Some Oxo-Acetate Bridged Trinuclear complexes. Influence of th Metal Oxidation State and Non-leaving Terminal Ligand (CO)." Bull.Chem.Soc.Jpn.65. 1411-1414 (1992)
[Publications] M.Abe: "X-Ray Structure,Ligand Substitution.and Other Properties of Trinuclcar Ruthenium Complex,〔Ru_3(μ_3-0)(μ- C_6H_5C00)_6(Py)_3〕(PF_6)(Pyridine).and X-Ray Say Structure of Dinuclear Rutheium Complcx.〔Ru_2(μ-C_6H_5C00)_4C1〕." Bull.Chem.Soc.Jpn.65. 1585-1590 (1992)
[Publications] K.Nakata: "Synthesis of Trinuclear Molybdenum Cluster Complex with Novel Skeleton.[MoxX_3(μX_3-O)(μ-CHX_3COO)X_6(CHX_3OH)X_3lCl Through Bridgeng Carboxylate Ligand substitution" Chem.Lett.983-986 (1992)
[Publications] K.Kabuto: "Absolute Configuration of Aldonic Acids and Lanthanoid Induced Shift by the Chiral Shift Reagent Propylenediaminetetraacetateeuropium(III) in Aqueous Solution." Tetragedron.Asymmetry. 3. 1357-1360 (1992)
[Publications] Y.Sasaki: "Mixed Chromium(III)-Ruthenium(III) Trinuclear Complex,[CrRu_2(μ_3-O)(μ-CH_3COO)_6(Pyridine)X_3]^+." Chem.Lett.69-72 (1993)
[Publications] C.Kabuto: "Unusual Hexameric Structure in the Crystal of Sodium Propylenediaminetetraacetatoeuropium(III)." J.Chem.Soc.,Chem.Commun.
[Publications] 大野弘幸: "ポリエチレンオキシド中の各種無機塩類の溶解とイオン伝導度に及ぼす連鎖分子量と塩類の効果(II)" 日本化学会誌. 552-557 (1992)
[Publications] H.Ohtaki: "Structure and dynamics of Solutions." Elsevier, 344 (1992)

1992 Fiscal Year Annual Research Report

溶液の非平衝過程の分子論的アプローチ・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.Ohtaki: "A Structural Study of Saturated Aqueous Solutions of Some Alkali Halides by X-Ray Diffraction" J.Solution Chem.21. 23-38 (1992)

[Publications] H.Ohtaki: "An Attempt to Parameterize the Structuredness of Solvents" J.Solution Chem.21. 39-47 (1992)

[Publications] K.Waizumi: "Structure of 2RbCl・CuClX_2・2HX_2O." Acta Crystallogr.C48. 1374-1376 (1992)

[Publications] K.Waizumi: "X-Ray Structural Studies of FebrX_2・4HX_2O,CoBrX_2O,NiClX_2D2・4HX_2O,and CuBrX_2・4HX_2O. Cis/trans Silictivity in Transition Metal(II)Dihalide Tetrahydrate." Inorg.Chim.Acta. 192. 173-181 (1992)

[Publications] T.Radnai: "X-Ray Diffraction Studies on the Structure of the Tri- and Tetrathiocyanatomanganate(II) Complexes and Solvated Lithium Ion in N,N-Dimethylformamide." Bull.Chem.Soc.Jpn.65. 1445-1452 (1992)

[Publications] K.Ozutsumi: "EXAFS and X-Ray Diffraction Studies on the Structure of the Tetrathiocyanatocadmate(II) Complex in Dimethyl Sulfoxide." Bull.Chem.Soc.Jpn.65. 2104-2113 (1992)

[Publications] K.Waizumi: "Density Function Calculations on the Geometries and Dissociation Energies of [M(HX_2O)X_6]X^<2+> Ions MX^<2+>=CrX^<2+>,MnX^<2+>,FeX^<2+>,CoX^<2+>,NiX^<2+>,CuX^<2+>,and ZnX^<2+>." Chem.Lett.1489-1492 (1992)

[Publications] T.Radnai: "Intramolecular and Liquid Structures of Tetramethylurea Studied by Means of X-Ray Diffraction." Z.Naturforsch.47a. 1003-1010 (1992)

[Publications] H.Ohtaki: "Dissolution and Nucleation Phenomena of Salts in Water.Molecular Dynamic Approaches and Supporting Solution X-Ray Diffraction Measurements." Pure&Appl.Chem.65. 203-211 (1993)

[Publications] S.Patnaik: "A Structural Study on AgI-AgX_2O-CrOX_3 Glass." J.Phys.Soc.Jpn.62. 536-543 (1993)

[Publications] S.Patnaik: "An X-Ray RDF Study of the Glass 30AgI-45AgX_2O-25 VX_2OX_5.Solid State Ionics." Solid State Ionics.

[Publications] H.Ohtaki: "Structure and Dynamics of Hydrated Ions." Chem.Rev.

[Publications] H.Ohtaki: "Molecular Aspects on the Dissolution and Nucleation of Ionic Crystals in Water." Adv.Inorg.Chem.

[Publications] H.Ohtaki: "Structure of Divalent Metal Complexes with Halide and Thiocyanate Ions in Solution." J.Indian Chem.Soc.

[Publications] Y.Shimizu: "Kinetic Studies of the Incorporation of the Zinc(II) Ioninto water-Soluble N-Phenyl-Substituted Porphyrins.Deformation Effect on the Metallation Rate." Bull.Chem.Soc.Jpn.65. 771-776 (1992)

[Publications] S.Soyama: "Variable-Temperature and -Pressure Multinuclear Magnetic Resonance Study on Solvent Exchange at Tris(ethylenediamine)nickel(II) Ione in Ethylenediamine." Inorg.Chem.31. 536-538 (1992)

[Publications] S.Funahashi: "High-Pressure Stopped-Flow Nuclear Magnetic Resonance Apparatus for the Study of Fast Reaction in Solution." Rev.Sci.Instrum.

[Publications] S.Aizawa: "Synthesis,Structural Characterization,and Metallation of N-o-Tolyl-5,10,15,20-tetraphenylporphine:Deformation Effect due to a Bulky N-Substituent Group." Inorg.Chem.

[Publications] S.Yamashita: "A New Laboratory XAFS Spectrometer for X-Ray Absorption Spectra of Light Elements." X-Ray Spectrometry. 21. 91-97 (1992)

[Publications] T.Takamuku: "Raman Spectroscopic and X-ray Diffraction Studies on Concentrated Aqueous Zinc(II) Bromide Solution at High Temperatures." Z.Naturforsch. 47a. 485-492 (1992)

[Publications] T.Takamuku: "Structure of Supercooled Aqueous Zinc(II) Bromide Solutions by Raman X-ray Scattering Methode." Z.Naturforsch. 47a. 841-848 (1992)

[Publications] T.Takamuku: "NMR Study on Dynamics of Water Molecules in Concentrated Aqueous Zinc(II) Bromide Solutions at Various Temteratures." J.Phys.Chem.96. 9487-9492 (1992)

[Publications] T.Kurisaki: "Temperature Effecrt on the Structure of Hydrated Lanthanide(II) Ions in Crystales and Solution." J.Alloys and Compounds.

[Publications] Y.Yamasaki: "Determination of the Absolute Configuration of Sodium(-)X_<589>-Bis(N-methyliminodiacetato)cobalt(III) Trihydrate." Acta Crystallogr.

[Publications] H.Wakita: "A XANES Study of Square Copper(II) Complexes." Advances in X-Ray Analysis. 35. 1115-1120 (1992)

[Publications] T.Yamaguchi: "Study on Stepwise Copper(II) Chloride Complexes in Acetonitrile by Fluorescence XAFS Spectroscopy Using Thermodynamic Data." Jap.J.Appl.Phys.

[Publications] T.Yamaguchi: "X-Ray Absorption Study on Aqueous Ionic Solutions in the Liquid and Glassy States." Jap.J.Appl.Phys.

[Publications] T.Yamaguchi: "XAFS Study with an In Situ Electrochemical Cell on Manganese Schiff Base Complexes as a Model of Photosystem II." Jap.J.Appl.Phys.

[Publications] H.Miki: "Phosphorescence from the Triplet Spin Sublevels of Hexanuclear Molybdemum(II) Chloride Cluster Ion,[MoX_6ClX_<14>]X^<2->.Relative Radiative Rate Constants for Emitting Sublevels." J.Phys.Chem.96. 3236-3239 (1992)

[Publications] M.Ebihara: "Syntheses,Structures and Properties of Pxidized Hexamolybdenum Clusters [(MoX_6XX_7Y)X'X_6]X^<2->(X=X'=Cl,Br;Y=S,Se)." Inorg.Chem.31. 1644-1649 (1992)

[Publications] M.Abe: "Kinetic Studies on the Terminal Phyridine Exchange Reaction of Some Oxo-Acetate Bridged Trinuclear complexes. Influence of th Metal Oxidation State and Non-leaving Terminal Ligand (CO)." Bull.Chem.Soc.Jpn.65. 1411-1414 (1992)

[Publications] M.Abe: "X-Ray Structure,Ligand Substitution.and Other Properties of Trinuclcar Ruthenium Complex,〔Ru_3(μ_3-0)(μ- C_6H_5C00)_6(Py)_3〕(PF_6)(Pyridine).and X-Ray Say Structure of Dinuclear Rutheium Complcx.〔Ru_2(μ-C_6H_5C00)_4C1〕." Bull.Chem.Soc.Jpn.65. 1585-1590 (1992)

[Publications] K.Nakata: "Synthesis of Trinuclear Molybdenum Cluster Complex with Novel Skeleton.[MoxX_3(μX_3-O)(μ-CHX_3COO)X_6(CHX_3OH)X_3lCl Through Bridgeng Carboxylate Ligand substitution" Chem.Lett.983-986 (1992)

[Publications] K.Kabuto: "Absolute Configuration of Aldonic Acids and Lanthanoid Induced Shift by the Chiral Shift Reagent Propylenediaminetetraacetateeuropium(III) in Aqueous Solution." Tetragedron.Asymmetry. 3. 1357-1360 (1992)

[Publications] Y.Sasaki: "Mixed Chromium(III)-Ruthenium(III) Trinuclear Complex,[CrRu_2(μ_3-O)(μ-CH_3COO)_6(Pyridine)X_3]^+." Chem.Lett.69-72 (1993)

[Publications] C.Kabuto: "Unusual Hexameric Structure in the Crystal of Sodium Propylenediaminetetraacetatoeuropium(III)." J.Chem.Soc.,Chem.Commun.

[Publications] 大野 弘幸: "ポリエチレンオキシド中の各種無機塩類の溶解とイオン伝導度に及ぼす連鎖分子量と塩類の効果(II)" 日本化学会誌. 552-557 (1992)

[Publications] H.Ohtaki: "Structure and dynamics of Solutions." Elsevier, 344 (1992)

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] 大野弘幸: "ポリエチレンオキシド中の各種無機塩類の溶解とイオン伝導度に及ぼす連鎖分子量と塩類の効果(II)" 日本化学会誌. 552-557 (1992)