1993 Fiscal Year Annual Research Report

錯形成反応機構の解明と速度論的分析法の開拓

Research Project

Project/Area Number	04403011
Research Institution	Nagoya University
Principal Investigator	舟橋重信名古屋大学, 理学部, 教授 (30022700)
Co-Investigator(Kenkyū-buntansha)	稲田康宏名古屋大学, 理学部, 助手 (60242814) 會澤宣一名古屋大学, 理学部, 助手 (60231099)
Keywords	速度論的分析法 / 溶媒和構造 / 溶媒交換反応 / ストップトフロー法 / EXAFS法
Research Abstract	溶液内反応に関与する化学種の溶液内構造やそれらの反応機構を解明し、明確にされた反応に立脚して、高選択性・高感度な速度論的分析法を系統的に開拓することが本研究の目的である。本年度は次のような成果を得た。 1.EXAFS法を用いて、大きさの異なる6種のニトリル中におけるNi(II)イオンとMn(II)イオンと、さらにプロパンジアミン中の二価の遷移金属イオンの溶媒和構造を明らかにした。その成果に基づいてNMR法を用いて溶媒交換反応速度を測定し、溶媒と金属イオンの大きさによる機構の変化を解明した。 2.直鎖状三座アミンを配位した各種Pd(II)錯体を合成し、その分子構造をX線回折法で明らかにした。さらにその錯体のアセトニトリルの交換速度をNMR法で研究し、遷移状態におけるキレート環の歪みや対イオンの効果が反応性に及ぼす影響を速度論的に明確にした。 3.アスコルビン酸およびその類似化合物とジシアノビス(1,10-フェナントロリン)鉄(III)との酸化還元反応、さらに、ヘキサシアノ鉄(III)、ルテニウム(III)およびオスミウム(III)酸イオンとアスコルビン酸との酸化還元反応を高圧力下でストップトフロー法を用いて測定し、外圈型酸化還元機構を解明した。アスコルビン酸ラジカルの反応性を明確にした。 4.ストップトフローEXAFS法を用いて、水銀(II)ポルフィリンと銅(II)イオンとの金属置換反応の過渡過程に存在する、短寿命不安定中間体である水銀(II)と銅(II)イオンをポルフィン環の上下に配位した二核ポルフィリン錯体中の銅(II)イオン周りの構造を明らかにした。これは本研究で進めている角度分散型のストップトフローEXAFS法の開発につながる大きな成果である。

Research Products
(10 results)

All Other

All Publications (10 results)

[Publications] S.Funahashi: "High-Pressure Stopped-Flow Nuclear Magnetic Resonance Apparatus for the Study of Fast Reactions in Solution" Review of Scientific Instruments. 64. 130-134 (1993)
[Publications] S.Aizawa: "Synthesis,Structural Characterization,and Metalation of N-o-Tolyl-5,10,15,20-tetraphenylporphine:Deformation Effect Due to a Bulky N-Substituent Group" Inorganic Chemistry. 32. 1119-1123 (1993)
[Publications] Y.Inada: "Structure of Copper(II) Ethylenediamine Complexes in Aqueous and Neat Ethylenediamine Solutions and Solvent-Exchange Kinetics of the Copper(II) Ion in Ethylenediamine As Studied by EXAFS and NMR Methods" Inorganic Chemistry. 32. 3010-3014 (1993)
[Publications] S.Aizawa: "Dissociative Path Promoted by Ion-Pair Formation for Acetonitrile Exchange Reaction of the Palladium(II) Complex with Diethylenetriamine" Chemistry Letters. 1607-1610 (1993)
[Publications] Y.Inada: "In-Laboratory Stopped-Flow Extended X-ray Absorption Fine Structure Apparatus in the Dispersive Mode for Determination of the Structure of Short-Lived Intermediates" Review of Scientific Instruments. 65. 18-24 (1994)
[Publications] H.Ohtaki: "Direct Structural Determination of the Short-Lived Intermediate Formed in Dynamic Processes of the Copper(II) Incorporation into Mercury(II) Porphyrin by the Newly Developed Stopped-Flow EXAFS Method" Journal of the Chemical Society,Chemical Communication. (in press.).
[Publications] Y.Inada: "Solvation Structures of Manganese(II),Iron(II),Cobalt(II),Nickel(II),Copper(II),Zinc(II),Cadmium(II),and Indium(III) Ions in 1,1,3,3-Tetramethylurea As Studied by EXAFS and Electronic Spectroscopy:Variation of Coordination Number" Inorganic Chemistry. (in press.).
[Publications] S.Aizawa: "Variable-Temperature and Variable-Pressure Sodium-23 NMR Study on Dissociation Reaction of Sodium(I) Cryptates in Ethylenesiamine" Bulletin of the Chemical Society of Japan. (in press.).
[Publications] N.Kagayama: "Mechanistic Study on the Reaction of L-Ascorbic Acid with Hexacyanometallate(III) of Iron(III),Ruthenium(III),and Osmium(III) Ions in Aqueous Acidic Solution at Elevated Pressures" Inorganic Chemistry. (in press.).
[Publications] S.Funahashi: "High Pressure Liquid and Solution,CJMR Vol.13" Elsevier(in press.),

1993 Fiscal Year Annual Research Report

錯形成反応機構の解明と速度論的分析法の開拓

Principal Investigator

舟橋 重信 名古屋大学, 理学部, 教授 (30022700)

Research Products

[Publications] S.Funahashi: "High-Pressure Stopped-Flow Nuclear Magnetic Resonance Apparatus for the Study of Fast Reactions in Solution" Review of Scientific Instruments. 64. 130-134 (1993)

[Publications] S.Aizawa: "Synthesis,Structural Characterization,and Metalation of N-o-Tolyl-5,10,15,20-tetraphenylporphine:Deformation Effect Due to a Bulky N-Substituent Group" Inorganic Chemistry. 32. 1119-1123 (1993)

[Publications] Y.Inada: "Structure of Copper(II) Ethylenediamine Complexes in Aqueous and Neat Ethylenediamine Solutions and Solvent-Exchange Kinetics of the Copper(II) Ion in Ethylenediamine As Studied by EXAFS and NMR Methods" Inorganic Chemistry. 32. 3010-3014 (1993)

[Publications] S.Aizawa: "Dissociative Path Promoted by Ion-Pair Formation for Acetonitrile Exchange Reaction of the Palladium(II) Complex with Diethylenetriamine" Chemistry Letters. 1607-1610 (1993)

[Publications] Y.Inada: "In-Laboratory Stopped-Flow Extended X-ray Absorption Fine Structure Apparatus in the Dispersive Mode for Determination of the Structure of Short-Lived Intermediates" Review of Scientific Instruments. 65. 18-24 (1994)

[Publications] H.Ohtaki: "Direct Structural Determination of the Short-Lived Intermediate Formed in Dynamic Processes of the Copper(II) Incorporation into Mercury(II) Porphyrin by the Newly Developed Stopped-Flow EXAFS Method" Journal of the Chemical Society,Chemical Communication. (in press.).

[Publications] Y.Inada: "Solvation Structures of Manganese(II),Iron(II),Cobalt(II),Nickel(II),Copper(II),Zinc(II),Cadmium(II),and Indium(III) Ions in 1,1,3,3-Tetramethylurea As Studied by EXAFS and Electronic Spectroscopy:Variation of Coordination Number" Inorganic Chemistry. (in press.).

[Publications] S.Aizawa: "Variable-Temperature and Variable-Pressure Sodium-23 NMR Study on Dissociation Reaction of Sodium(I) Cryptates in Ethylenesiamine" Bulletin of the Chemical Society of Japan. (in press.).

[Publications] N.Kagayama: "Mechanistic Study on the Reaction of L-Ascorbic Acid with Hexacyanometallate(III) of Iron(III),Ruthenium(III),and Osmium(III) Ions in Aqueous Acidic Solution at Elevated Pressures" Inorganic Chemistry. (in press.).

[Publications] S.Funahashi: "High Pressure Liquid and Solution,CJMR Vol.13" Elsevier(in press.),

舟橋重信名古屋大学, 理学部, 教授 (30022700)