1995 Fiscal Year Annual Research Report

溶液錯体化学の新しい領域を拓く-「超分子効果」の前駆現象として捉える立場から-

Research Project

Project/Area Number	07304045
Research Category	Grant-in-Aid for Co-operative Research (A)
Research Institution	Osaka University
Principal Investigator	海崎純男大阪大学, 理学部, 教授 (20089874)
Co-Investigator(Kenkyū-buntansha)	石原浩二早稲田大学, 理工学部, 教授 (20168248) 澤田清新潟大学, 理学部, 教授 (40089850) 石黒慎一九州大学, 理学部, 教授 (80111673) 飯田雅康奈良女子大学, 理学部, 教授 (00107343) 舟橋重信名古屋大学, 理学部, 教授 (30022700)
Keywords	超分子効果 / メゾスコピック / ミセル系 / 溶媒和構造 / 配位子置換反応 / 酸化還元反応
Research Abstract	研究報告会で総合討論された以下の内容の一部と題目に示すような課題について、総合研究のテーマを視野に入れながら、研究を展開している。内容1)μ-oxoRu(III)複核錯体の,(lll,ll)と(ll,ll)へのアセトニトリル溶液中での還元電位が,プロトン供与体やBF_3のルイス酸のμ-oxoへの付加で大きく正側(ca1Vも)にシフトし、プロトン供与体のpKaの違いにより,このシフトや関与する電子数を制御できることが明らかとなった。(佐々木) 2)[VO(salenO)]_2(CH_2)_n(n=3,6,10,12)錯体とFe(lll)との酸化還元速度に対するメチレン鎖の効果はメチレン鎖(n)の増加に伴って、活性化エンタルピーと活性化エントロピーがともに増大し、両者の間に補償効果が見られた。(阿部) 題目:(1)メチル白金(IV)錯体の配位子置換反応(石原)(2)ミセル界面での特異的錯形成(石黒)(3)塩化ナトリウムによる水-アセトニトリル混合溶媒の液体構造の変化とイオン対抽出機構(田端)(4)非極性溶媒中のポリエーテル錯体のイオン対平衡とその構造(澤田)(5)有機スズ(IV)化合物の結晶構造と溶存状態(舟橋)(6)高配位ケイ素(IV)錯体の立体化学(吉川)(7)極性非水溶媒中におけるコバルト(ll)イオンの溶媒和構造(横山)(8)非配位カルボキシル基を持つ[Co(edta)]-型錯体からの両親媒性錯体の合成(小稲)(9)金属錯体と溶媒間の協同的相互作用(岩本)(10)ラマン分光法による錯体溶液構造の研究(金森)(11)非水溶媒中におけるアルカリ金属イオンと18-クラウン-6の錯形成(小堤)(12)cis-[CrF_2(N)_4]型錯体のソルバトクロミズムと2H NMRスペクトルの溶媒依存性(海崎)(13)ミセル系での金属錯イオンの挙動に関する研究(飯田)

Research Products

(15 results)

All Other

All Publications (15 results)

[Publications] Yukiko Terasaki: "Solvent-dependent ^2H NMR spectra and solvatochromism in liagnd field absorption bands of cis-[CrF_2N_4]type complexes with trimethylenetetramine pyridine and 22′-bipyridine" J.Chem.Soc.Dalton Trans.1995. 2837-2841 (1995)
[Publications] S.Aizawa: "Variable-Temperature and-Pressure Multinuclear Magnetic Resonance Studies on Solvent Exchange of Cobalt(ll),Iron(ll)、and Manganese(ll)lons in Ethylenediamine.Kinetic Chelate Effect and Chelate Strain Effect" Inorg.Chem.34. 2042-2047 (1995)
[Publications] M.Iida: "^<59>Co NMR Spectroscopic Chiral Discrimination of[Co(en)_3]^<3t> Enantiomers in Ionic Interacting Systems" Bull.Chem.Soc.Jpn.68. 1337-1344 (1995)
[Publications] M.Koide: "Molar Enthalpy of Transfer of Divalent Transition Metal Ions and Their Chloro Complexes from N,N-Dimethylformamide to N,N-Dimethylacetamide" J.Solution Chem.24. 511-522 (1995)
[Publications] K.Sawada: "Ion-pair of tetraalkylammonium picrate" J.Mol.Liquids. 65/66. 266-268 (1996)
[Publications] Takashi Fujihara: "Base Hydrolysis in Homometallic Dinuclear Chromium(lll) Complexes Bridged by Hydroxide and Carboxyrate" J.Chem.Soc.Dalton Trans.1995. 1823-1831 (1995)
[Publications] Yuichi Kondo: "Kinetic Study of the Reaction of Tetramethylplatinum(IV)Complexes with Acids" Ionrg.Chim.Acta. 241. 81-85 (1996)
[Publications] Akihiro Kikuchi: "Redox Behaviour of the Oxo-bridged Diruthebnium Complex,[Ru_2(μ-O)(μ-MeCO_2)_2(bpy)_2(mim)_2]^<2+>in Acetonitrile in the Presence of Various Proton Donors(bpy=2,2′-bipyridine,mim=1-methylimidazole)" J.Chem.Soc.,Chem.Commun.1995. 2125-2126 (1995)
[Publications] Masaaki Tabata: "Kinetics and Mechanism of Metal-Substitution Reaction of Homodinuclear Mercury(ll) Porphyrin with Zinc(ll) with Particular Reference to a Heterodinuclear Metalloporphyrin Intermediate" Inog.Chem.34. 6492-6496 (1995)
[Publications] E.Iwamoto: "Cooperative interactions between ions and water in the chloride ion and water coordination to a square-planar nickel complex ion in concentrated aqueous solutions" J.Chem.Soc.Faraday Trans.91. 627-630 (1995)
[Publications] K.Ozutsumi: "Structure of the Monohalogenocadmium(ll) Complexes in N,N-Dimethylformamide" J.Mol.Liquids,. 65/66. 361-364 (1995)
[Publications] Haruhiko Yokoyama: "X-Ray Diftraction Study of Solvation Structure of the Cobalt(ll) lon in N,N-Dimethylformamide Solution" Z.Naturforsch.50a. 301-306 (1995)
[Publications] F.MD.Akhter: "Photochemical Desulfurization of a Sulfinate-S-Cobalt(lll) Complex.Formation of an Organic Peroxide Complex" Chem.Lett.1996. 81-82 (1996)
[Publications] M.Iida: "Appreciable Effects of lon-Pairing on the ^<59>Co Electric Field Gradients in the NMR Relaxations of[Co(chxn)_3]^<3+>" J.Phys.Chem.99. 4347-4352 (1995)
[Publications] Kan Kanamori: "Syntheses,Characterization,and Properties of Vanadium(lll) Complexes Containing Tripodal Tetradentate Ligands with Single Pyridy Groups" Bull.Chem.Soc.Jpn.68. 2581-2589 (1995)

1995 Fiscal Year Annual Research Report

溶液錯体化学の新しい領域を拓く-「超分子効果」の前駆現象として捉える立場から-

Principal Investigator

海崎 純男 大阪大学, 理学部, 教授 (20089874)

Research Products

[Publications] Yukiko Terasaki: "Solvent-dependent ^2H NMR spectra and solvatochromism in liagnd field absorption bands of cis-[CrF_2N_4]type complexes with trimethylenetetramine pyridine and 22′-bipyridine" J.Chem.Soc.Dalton Trans.1995. 2837-2841 (1995)

[Publications] S.Aizawa: "Variable-Temperature and-Pressure Multinuclear Magnetic Resonance Studies on Solvent Exchange of Cobalt(ll),Iron(ll)、and Manganese(ll)lons in Ethylenediamine.Kinetic Chelate Effect and Chelate Strain Effect" Inorg.Chem.34. 2042-2047 (1995)

[Publications] M.Iida: "^<59>Co NMR Spectroscopic Chiral Discrimination of[Co(en)_3]^<3t> Enantiomers in Ionic Interacting Systems" Bull.Chem.Soc.Jpn.68. 1337-1344 (1995)

[Publications] M.Koide: "Molar Enthalpy of Transfer of Divalent Transition Metal Ions and Their Chloro Complexes from N,N-Dimethylformamide to N,N-Dimethylacetamide" J.Solution Chem.24. 511-522 (1995)

[Publications] K.Sawada: "Ion-pair of tetraalkylammonium picrate" J.Mol.Liquids. 65/66. 266-268 (1996)

[Publications] Takashi Fujihara: "Base Hydrolysis in Homometallic Dinuclear Chromium(lll) Complexes Bridged by Hydroxide and Carboxyrate" J.Chem.Soc.Dalton Trans.1995. 1823-1831 (1995)

[Publications] Yuichi Kondo: "Kinetic Study of the Reaction of Tetramethylplatinum(IV)Complexes with Acids" Ionrg.Chim.Acta. 241. 81-85 (1996)

[Publications] Akihiro Kikuchi: "Redox Behaviour of the Oxo-bridged Diruthebnium Complex,[Ru_2(μ-O)(μ-MeCO_2)_2(bpy)_2(mim)_2]^<2+>in Acetonitrile in the Presence of Various Proton Donors(bpy=2,2′-bipyridine,mim=1-methylimidazole)" J.Chem.Soc.,Chem.Commun.1995. 2125-2126 (1995)

[Publications] Masaaki Tabata: "Kinetics and Mechanism of Metal-Substitution Reaction of Homodinuclear Mercury(ll) Porphyrin with Zinc(ll) with Particular Reference to a Heterodinuclear Metalloporphyrin Intermediate" Inog.Chem.34. 6492-6496 (1995)

[Publications] E.Iwamoto: "Cooperative interactions between ions and water in the chloride ion and water coordination to a square-planar nickel complex ion in concentrated aqueous solutions" J.Chem.Soc.Faraday Trans.91. 627-630 (1995)

[Publications] K.Ozutsumi: "Structure of the Monohalogenocadmium(ll) Complexes in N,N-Dimethylformamide" J.Mol.Liquids,. 65/66. 361-364 (1995)

[Publications] Haruhiko Yokoyama: "X-Ray Diftraction Study of Solvation Structure of the Cobalt(ll) lon in N,N-Dimethylformamide Solution" Z.Naturforsch.50a. 301-306 (1995)

[Publications] F.MD.Akhter: "Photochemical Desulfurization of a Sulfinate-S-Cobalt(lll) Complex.Formation of an Organic Peroxide Complex" Chem.Lett.1996. 81-82 (1996)

[Publications] M.Iida: "Appreciable Effects of lon-Pairing on the ^<59>Co Electric Field Gradients in the NMR Relaxations of[Co(chxn)_3]^<3+>" J.Phys.Chem.99. 4347-4352 (1995)

[Publications] Kan Kanamori: "Syntheses,Characterization,and Properties of Vanadium(lll) Complexes Containing Tripodal Tetradentate Ligands with Single Pyridy Groups" Bull.Chem.Soc.Jpn.68. 2581-2589 (1995)

海崎純男大阪大学, 理学部, 教授 (20089874)