1995 Fiscal Year Annual Research Report

有機スズ(IV)化合物のスペシエーションと光分解反応の解明

Research Project

Project/Area Number	07454199
Research Category	Grant-in-Aid for General Scientific Research (B)
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)	會澤宣一名古屋大学, 理学部, 助手 (60231099)
Keywords	有機スズ(IV) / スペシエーション / 錯形成反応 / トリフェニルスズ(IV)ラジカル / アルキルスズ(IV)化合物
Research Abstract	本年度の研究成果を以下のように3つに分けて報告する。 (A)有機スズ(IV)のスペシエーション (a)電位差滴定法による加水分解平衡の測定 R_3Sn^+,R_2Sn^<2+>(R:Et,Me)の加水分解平衡定数を決定した。ヒドロキソ架橋の多量体が生成する。その構造と多量体生成の関係を明らかにした。 (b)電位差滴定法による錯形成反応の生成定数の決定 R_2Sn^<2+>,RSn^<3+>(R:Et,Me)とアミノポリカルボン酸(NTA,EDDA,MIDA,PDA)や塩化物イオン、炭酸イオン、酢酸イオン、リン酸イオンとの錯形成反応に関する平衡定数を決定した。Rの電子供与性や配位子の塩基性との関係を定量的に明らかにし、またキレート形成の有無を構造の観点から検証した。 (B)有機スジ(IV)化合物の構造の決定 (a)単結晶の生成と結晶解析 (Me)_2Sn^<2+>とNTA,EDDA,MIDA,PDAとの結晶を得ることに成功し、その結晶構造を決定した。スズ原子は2配位、3配位、4配位、5配位、6配位、7配位と多様な配位数を取り、それは配位子とのσ結合性と密接な関係にあることを明らかにした。 (b)スズ(IV)化合物のEXAFSスペクトルの測定数百ミリモルの濃度で、1ないし2の化学種のみが溶存する条件を選び、EXAFSスペクトルを測定することによってスズ原子周りの構造を決定した。 (C)レーザー光分解反応による有機スズのスペシエーションメチルスズ(IV)とテトラフェニルスズ(IV)のYAGレーザー照射による光分解の反応機構を研究した。トリフェニルスズラジカルの動的挙動を明らかにした。以上の研究計画通りに遂行することができた。

Research Products
(10 results)

All Other

All Publications (10 results)

[Publications] Shuji Kagawa: "Kinetic Study on Complexation of Boric Acid with 4-Isopropyltropolone in Nonaqueous Solution" Inorganica Chimica Acta. 231. 115-119 (1995)
[Publications] Sen-ichi Aizawa: "Variable-Temperature and-Pressure Multinuclear Magnetic Resonance Studies on Solvent Exchange of Cobalt (II),Iron (II),and Manganese (II) Ions in Ethylenediamine" Inorganic Chemistry. 34. 2042-2047 (1995)
[Publications] Hideo D Takagi: "Mechanistic Study of Oxidation Reaction of Hydroquinone,Catechol,and L-Ascorbic Acid by Dicyanobis(1,10-phenanthroline)iron (III) in Dimethyl sulfoxide" Journal of Molecular Liquids. 65/66. 277-280 (1995)
[Publications] Sen-ichi Aizawa: "Crystal Structures of Trifluoromethanesulfonato Complexes of Nickel (II) and Palladium (II), [Ni(bpy)_2 (CF_3SO_3)_2] and [Pd (triphosphine) (CF_3SO_3)・C_6H_6,and Characterization of the Coordination Ability of CF_3SO_3" Analytical Science. 11. 557-562 (1995)
[Publications] Masahiko Inamo: "Reactivity of Five-Coordinate Intermediate generated by Laser Photolysis of Monoligated Chloro(5,10,15,20-teraphenylporphinato)chromium (III) in Toluene" Bulletin of the Chemical Society of Japan. 68. 2293-2303 (1995)
[Publications] Sen-ichi Aizawa: "Characterization of σ and π Donation of Solvents by ^<31>PNMR Chemical Shifts of Trigonal-Bipyramidal Palladium (II) Complexes with Tris (2-diphenylphosphinoethyl)phosphine" Analytical Science. 12. 27-230 (1996)
[Publications] Mitsuru Matsumoto: "Oxidation Reaction of L-Ascorbic Acid by Dicyanobis (1,10-phenanthroline) iron (III) in Dimethyl Sulfoxide at Elevated Pressures.Evidence for the Adiabatic Electron Transfer" Inorganica Chimica Acta. (in press). (1996)
[Publications] Sen-ichi Aizawa: "Nitrogen-14 NMR Study on Solvent Exchange of Octahedral Cobalt (II) Ion in Neat 1,3-Propanediamine and n-Propylamine at Various Temperatures and Pressures" Inorganic Chimistry. (in press). (1996)
[Publications] Sen-ichi Aizawa: "Complexation Equilibria and Structures of Dimethyltin (IV) Complexes with N-Methyliminodiacetate,Pyridine-2,6-dicarboxylate,Ethylenediamine-N,N′-diacetate and Ethylenediamine-N,N,N′,N′-tetraacetate" Inorganica Chimica Acta. (in press). (1996)
[Publications] 舟橋重信: "詳説無機化学" 講談社,

1995 Fiscal Year Annual Research Report

有機スズ(IV)化合物のスペシエーションと光分解反応の解明

Principal Investigator

舟橋 重信 名古屋大学, 理学部, 教授 (30022700)

Research Products

[Publications] Shuji Kagawa: "Kinetic Study on Complexation of Boric Acid with 4-Isopropyltropolone in Nonaqueous Solution" Inorganica Chimica Acta. 231. 115-119 (1995)

[Publications] Sen-ichi Aizawa: "Variable-Temperature and-Pressure Multinuclear Magnetic Resonance Studies on Solvent Exchange of Cobalt (II),Iron (II),and Manganese (II) Ions in Ethylenediamine" Inorganic Chemistry. 34. 2042-2047 (1995)

[Publications] Hideo D Takagi: "Mechanistic Study of Oxidation Reaction of Hydroquinone,Catechol,and L-Ascorbic Acid by Dicyanobis(1,10-phenanthroline)iron (III) in Dimethyl sulfoxide" Journal of Molecular Liquids. 65/66. 277-280 (1995)

[Publications] Sen-ichi Aizawa: "Crystal Structures of Trifluoromethanesulfonato Complexes of Nickel (II) and Palladium (II), [Ni(bpy)_2 (CF_3SO_3)_2] and [Pd (triphosphine) (CF_3SO_3)・C_6H_6,and Characterization of the Coordination Ability of CF_3SO_3" Analytical Science. 11. 557-562 (1995)

[Publications] Masahiko Inamo: "Reactivity of Five-Coordinate Intermediate generated by Laser Photolysis of Monoligated Chloro(5,10,15,20-teraphenylporphinato)chromium (III) in Toluene" Bulletin of the Chemical Society of Japan. 68. 2293-2303 (1995)

[Publications] Sen-ichi Aizawa: "Characterization of σ and π Donation of Solvents by ^<31>PNMR Chemical Shifts of Trigonal-Bipyramidal Palladium (II) Complexes with Tris (2-diphenylphosphinoethyl)phosphine" Analytical Science. 12. 27-230 (1996)

[Publications] Mitsuru Matsumoto: "Oxidation Reaction of L-Ascorbic Acid by Dicyanobis (1,10-phenanthroline) iron (III) in Dimethyl Sulfoxide at Elevated Pressures.Evidence for the Adiabatic Electron Transfer" Inorganica Chimica Acta. (in press). (1996)

[Publications] Sen-ichi Aizawa: "Nitrogen-14 NMR Study on Solvent Exchange of Octahedral Cobalt (II) Ion in Neat 1,3-Propanediamine and n-Propylamine at Various Temperatures and Pressures" Inorganic Chimistry. (in press). (1996)

[Publications] Sen-ichi Aizawa: "Complexation Equilibria and Structures of Dimethyltin (IV) Complexes with N-Methyliminodiacetate,Pyridine-2,6-dicarboxylate,Ethylenediamine-N,N′-diacetate and Ethylenediamine-N,N,N′,N′-tetraacetate" Inorganica Chimica Acta. (in press). (1996)

[Publications] 舟橋重信: "詳説無機化学" 講談社,

舟橋重信名古屋大学, 理学部, 教授 (30022700)