1998 Fiscal Year Annual Research Report

精密EXAFS解析による溶存化学種の非調和原子間ポテンシャルの導出

Research Project

Project/Area Number	10874081
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)
Keywords	EXAFSスペクトル / 温度可変 / 非調和原子間ポテンシャル / 第一遷移金属(II)イオン / 溶媒和構造 / 非水溶媒 / 溶媒交換反応 / 活性化パラメーター
Research Abstract	本研究では、これまでに決定されている溶媒交換反応や配位子置換反応の活性化パラメーターの値に対して、各種溶媒中における金属イオンの溶媒和構造と金属-配位原子間の原子間非調和ポテンシャルを求めることにより、速度論的データの定量的解釈を行うことを目的とした。本年度は、温度可変EXAFSセルを用いて高エネルギー加速器研究機構・物質構造科学研究所・放射光研究施設のフォトンファクトリーにおいて温度可変EXAFSスペクトル測定を遂行した。具体的には、Mn(II)、Fe(II)、Co(II)およびNi(II)イオンの水、N,N-ジメチルホルムアミド(DMF)、1,1,3,3-テトラメチル尿素(TMU)およびアセトニトリル(AN)溶液のEXAFSスペクトルを、約0°Cから常圧での溶媒の沸点付近まで温度を変えて測定した。現時点で得られているEXAFSスペクトルからは、原子間非調和ポテンシャルを精度良く求めることには成功していないが、非調和ポテンシャルパラメーターに由来するEXAFS振動の変化が定性的に観測された。この変化は金属(II)イオンの種類によって大きく異なり、また、溶媒によっても著しい差異が認められた。特に、酸素原子で配位する水やDMF中に比べ、窒素原子で配位するAN中においては、ポテンシャルの非調和性が高いと示唆される結果を得た。また、TMU中におけるCo(II)-O原子間ポテンシャルが他の酸素配位する溶媒中よりも大きな非調和性を示すことが示唆されており、配位数の減少した溶媒和環境における会合的反応性をエネルギー論的に説明する情報を得た。これらの研究実績から、次年度でより温度範囲を広げたEXAFS測定を行うことにより、原子間非調和ポテンシャルの導出ができるとの確信を得た。

Research Products

(14 results)

All Other

All Publications (14 results)

[Publications] 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 Trimethylphosphate As Studied by EXAFS and Electronic Spectroscopies" The Journal of Physical Chemistry. in press. (1999)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] T.Yagyu: "Electronic Effect of Substituents on Cyciopalladation of the Solvated Palladium (II) Complexes with N-Benzyl Triamine [Pd(Sol)(4-XC_6H_4CH_2)NH(CH_2)_3NR(CH_3)_3NH_2]^<2+> (Sol=Solvent ; R=Ph, H, and Me ; X=H, Et, Me, MeO, Cl, and NO_2)" Bulletin of the Chemical Society of Japan. 71・8. 1857-1862 (1998)
[Publications] 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)
[Publications] 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)
[Publications] 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-Dimethylformamide" Main Group Chemistry. 2. 215-219 (1998)
[Publications] Y.Inada: "Development of Time-Resolved Stopped-Flow EXAFS Apparatus and Structure Determination of Shor-Lived Reaction Intermediates Formed in Dynamic Process of Inorganic Reactions in Solution" Recent Research Developments in Pure & Applied Chemistry. 2. 347-359 (1998)
[Publications] 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)
[Publications] Y.Inada: "Measurements of Fast Reactions in Solution by the Stopped-Flow Technique" Bunseki. 9. 647-654 (1998)
[Publications] 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)
[Publications] Y.Tsutsui: "The Stability of Seven-Coordinate Species of 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)
[Publications] 舟橋重信: "無機溶液反応の化学" 裳華房, 271 (1998)

1998 Fiscal Year Annual Research Report

精密EXAFS解析による溶存化学種の非調和原子間ポテンシャルの導出

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: "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 As Studied by EXAFS and Electronic Spectroscopies" The Journal of Physical Chemistry. in press. (1999)

[Publications] 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)

[Publications] 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)

[Publications] 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)

[Publications] 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)

[Publications] 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-Dimethylformamide" Main Group Chemistry. 2. 215-219 (1998)

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

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

[Publications] 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)

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

舟橋重信名古屋大学, 大学院・理学研究科, 教授 (30022700)

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