1999 年度実績報告書

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

研究課題

研究課題/領域番号	10874081
研究機関	名古屋大学
研究代表者	舟橋重信名古屋大学, 大学院・理学研究科, 教授 (30022700)
研究分担者	稲田康宏名古屋大学, 物質科学国際研究センター, 助手 (60242814)
キーワード	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
研究概要	本研究では、NMR法やストップトフロ一法などを用いて決定されている溶液内における金属イオンの溶媒交換反応や配位子置換反応の熱力学的な活性化パラメーターの値に関して、各種溶媒中における金属イオンの溶媒和構造と金属-配位原子間の原子問非調和ポテンシャルをEXAFS法を用いて決定することにより、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、改良した耐圧温度可変EXAFSセルを用いて、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で測定した広範な温度範囲のEXAFSスペクトルを、FEFF理論標準を用いて精密に解析した。具体的には、Fe(II)、Fe(III)、Co(II)、Ni(II)およびZn(II)イオンの水、1,1,3,3-テトラメチル尿素(TMU)およびアセトニトリル(AN)溶液に約100気圧の圧力をかけた状態で、約0℃から約300℃の範囲で温度を変化させてEXAFSスペクトルを測定した。これらを解析し、金属-配位原子間の結合距離、2次キュムラント項であるDebye-Waller因子、および、3次キュムラント項の温度依存性を決定した。これらのパラメーターから、金属-配位原子間のポテンシャル関数をモース型で取り扱ったときのポテンシャルパラメーターを決定した。これらの値は金属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ことが明らかになった。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ことができた。

研究成果

(15件)

すべてその他

すべて文献書誌 (15件)

[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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-dimethyl-1,10-phenanthroline)copper(I/II)in Acetonitrile"Inorganic Chemistry. 38・14. 3352-3360 (1999)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] M.Matsumoto,S.Funahashi,and H.D.Takagi: "Electrochemical Electron Transfer reactions of M(ttcn)^<3+/2+>_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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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+/+>_2with Ru(hexafluoroacetylacetone)^<0/->_3"Chemical Physics Letters. 306. 291-296 (1999)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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 年度 実績報告書

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

研究代表者

舟橋 重信 名古屋大学, 大学院・理学研究科, 教授 (30022700)

研究成果

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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-dimethyl-1,10-phenanthroline)copper(I/II)in Acetonitrile"Inorganic Chemistry. 38・14. 3352-3360 (1999)

[文献書誌] 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)

[文献書誌] M.Matsumoto,S.Funahashi,and H.D.Takagi: "Electrochemical Electron Transfer reactions of M(ttcn)^<3+/2+>_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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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+/+>_2with Ru(hexafluoroacetylacetone)^<0/->_3"Chemical Physics Letters. 306. 291-296 (1999)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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 年度実績報告書

舟橋重信名古屋大学, 大学院・理学研究科, 教授 (30022700)