1992 Fiscal Year Annual Research Report

高機能をめざした金属錯体構造の精密制御

Research Project

Project/Area Number	04303005
Research Institution	Kyushu University
Principal Investigator	大川尚士九州大学, 理学部, 教授 (00037219)
Co-Investigator(Kenkyū-buntansha)	宮本健東京大学, 理学部, 助教授 (30011604) 宗像恵近畿大学, 理工学部, 教授 (80090942) 巽和行大阪大学, 基礎工学部, 助教授 (10155096) 上原章金沢大学, 理学部, 教授 (30019484) 伊藤翼東北大学, 理学部, 教授 (90007328)
Keywords	分子強磁性体 / タングステン酸化環元酵素 / 抗腫瘍性白金錯体 / 伝導性錯体 / スイッチング機能 / ヘムエリトリン / カルコゲニド錯体 / 複合系錯体
Research Abstract	本研究班を4つ主題についてグループに分けて、以下の実積をあげた。 1.単核錯体の構造精密制御と高機能化:上山はタングステン酸化環元酵素の活性中心のモデルの化合物の合成して構造を明かにし、海崎はクロム(III)二核錯体の構造異性化の機構解明と体本化学的制御を、田中はルテニウム(II)錯本による二素化炭素の活性化とホルムアルデヒドおよびギ酸への変換を実現した。宮本は高い抗腫瘍活性を有する新しいシスプラチン類縁体を合成し、矢野は金属錯本をヘッドグループとする新しい界面活性剤の設計・開発を行った。 2.オリゴマー錯体の構造精密制御と高機能化:上原はヘムエリトリン数似機能を有する二核鉄(II)錯体の合成と酸素機構の解明を、芳賀はベンツイミダゾールを配位基とする二核ルテニウム錯体の合成とプロトン移動を伴うスイッチング機能を発現させた。福田はテトラケトナト架橋二核銅(II)およびニッケル(II)錯体がクロモトロビズムを示すことを明らかにした。 3.クラスター錯体の構造精密制御と高機能化:伊藤は多電子酸化環元過程を可能とするルテニウム錯体とポルフィリンからなる複合系錯体の設計に成功し、佐々木は分子不斉を有する最初のMo(V)W(V)クラスター錯体として[MoV(μ-O)(μ-S)(O)_2(edta)]^<2->の合成に成功した。巽は半サンドイッチ型タンタルカルコゲニド錯体を前駆体として新奇異核クラスター錯体の合成法を確立した。 4.大川はシュウ酸架橋ヘテロ金属三次元集合体を基本骨格とする分子強磁性体の設計法を確立し、大瀧はAglをドープした超イオン伝導性ガラスのイオン伝導機構をEXA母Sで研究した。西出は固相膜に修飾ポルフィリンを担持させた系を開発して酸素促進輸送を実現し、宗像は銅および銀錯体を集積させた化合物で伝導性を実現させた。

Research Products
(18 results)

All Other

All Publications (18 results)

[Publications] Hiroko TAMAKI: "Design of meta-complex Magnets.Synthesis and Magnetic Properties of Mixed-Metal Assemblies {NBu_4[MCr(ox)_3]}x" J.Am.Chem.Soc.114. 6974-6979 (1992)
[Publications] Hiroko TAMAKI: "Metal-complex Ferrimagnets with the Formula {NBu_4[MFe(ox)_3]}x" Chem.Lett.1992. 1975-1978 (1992)
[Publications] Nobutoshi KOMEDA: "Electrochemical Carbon Dioxide Fixation to Thioesters Catalyzed by [Mo_2Fe_6S_8(SEt)_9]^<3->" J.Am.Chem.Soc.114. 3625-3630 (1992)
[Publications] Nobutoshi KOMEDA: "A New Model for Dioxygen Binding in Hemoxyanin. Molecular Structure of μ-η^2;η^2 Preroxo Dinuclear Cu(II) Complexes" J.Am.Chem.Soc.114. 1278-1291 (1992)
[Publications] Norikazu UEYAMA: "cis-Dioxobis(benzenedithiolato)tungsten(V) nad related Monooxotungsten(V) and-(IV) Complexes.Model of Tungsten Oxidoreductases" J.Am.Chem.Soc.114. 7310-7311 (1992)
[Publications] Masatasu SUZUKI: "(μ-Alkoxo\diiron(II,II) Complexes of Tetrakis(2-(6-methylpyridyl)methyl)-1,3-diaminopropane-2-olate and Reversible Formation of O_2-adducts" Chem.Lett. 1992. 91-94 (1992)
[Publications] S.Patnaik: "A Structural Study on AgI-Ag_2O-CrO_3" J.Phys.Soc.Jpn.62. 536-543 (1992)
[Publications] Masahiro EBIHARA: "Synthesis,Structure,and Properties of Oxidized Hexamolybodenum Clusters" Inorg.Chem.31. 1645-1649 (1992)
[Publications] Michiko SATO: "Anion Sensing Electrodes Based on Nickel(II) Mixed Ligand Complexes" Chem.Lett.1992. 399-402 (1992)
[Publications] MAsayuki KOIKAWA: "Synthesis and Characterization of Fe(III) and Fe(IV) Complexes of N-(o-Hydroxyphenyl)salicylamide and Homologs" Inorg. Chim.Acta. 194. 75-80 (1992)
[Publications] Kenji SHINDO: "A Manganese(III) Complex of 3,5-Bis((salicylidene-amino)methyl)pyrazole:Synthesis,Structure,and Properties" Inorg.Chem.31. 4987-4990 (1992)
[Publications] Masaaki OHBA: "Synthesis and Magnetisms of Oxamido-and Oxamato-bridged Nickel(II)-Copper(II) Complexes" Bull.Chem.Soc.Jpn.65. 1988-1989 (1992)
[Publications] Megumu MUNAKATA: "Synthesis,Structures and Formation Constants of Cu(I) Complexes with Alkynes and 1,10-Phenanthroline" J.Chem.Soc.,Dalton Trans.1992. 2225-2230 (1992)
[Publications] Manabu NAKAHANADA: "Synthesis and Characterization of L-Tartrato Chromate(III) Complexes with Acetylacetonate Ions" J.Chem.Soc.,Dalton Trans.1992. 3423-3426 (1992)
[Publications] Yuzo NISHIDA: "Reaction Between Binuclear Iron(III) Compounds and DMPO (5,5-Dimethy1-3,5-dihydropyrrole N-Oxide)" J.Chem.Soc.,Chem.Commun. 1992. 93-94 (1992)
[Publications] Masaaki HAGA: "Photoexcited States of Biruthenium(II) Compounds Bridged by 2,2'-Bis(2-pyridyl)bibenzimidazole" Inorg.Chem.31. 548-555 (1992)
[Publications] Takashi MIYAMOTO: "Stability and Reactivity of Dihydroxobis(trimethy1-phosphine)platinum(II),an Intermediate Species for the Synthesis of Water-Soluble Phosphine Complexes" Bull.Chem.Soc.Jpn.65. 3386-3397 (1992)
[Publications] Koshiro TORIUMI: "Phase Transitions of the Halogen-Bridged M^<II>-X-M^<IV> Mixed-Valence Complexes[M(en)_2][MX_2(en)_2](ClO_4)_2" Acta Crystallogr.1992. (1992)

1992 Fiscal Year Annual Research Report

高機能をめざした金属錯体構造の精密制御

Principal Investigator

大川 尚士 九州大学, 理学部, 教授 (00037219)

Research Products

[Publications] Hiroko TAMAKI: "Design of meta-complex Magnets.Synthesis and Magnetic Properties of Mixed-Metal Assemblies {NBu_4[MCr(ox)_3]}x" J.Am.Chem.Soc.114. 6974-6979 (1992)

[Publications] Hiroko TAMAKI: "Metal-complex Ferrimagnets with the Formula {NBu_4[MFe(ox)_3]}x" Chem.Lett.1992. 1975-1978 (1992)

[Publications] Nobutoshi KOMEDA: "Electrochemical Carbon Dioxide Fixation to Thioesters Catalyzed by [Mo_2Fe_6S_8(SEt)_9]^<3->" J.Am.Chem.Soc.114. 3625-3630 (1992)

[Publications] Nobutoshi KOMEDA: "A New Model for Dioxygen Binding in Hemoxyanin. Molecular Structure of μ-η^2;η^2 Preroxo Dinuclear Cu(II) Complexes" J.Am.Chem.Soc.114. 1278-1291 (1992)

[Publications] Norikazu UEYAMA: "cis-Dioxobis(benzenedithiolato)tungsten(V) nad related Monooxotungsten(V) and-(IV) Complexes.Model of Tungsten Oxidoreductases" J.Am.Chem.Soc.114. 7310-7311 (1992)

[Publications] Masatasu SUZUKI: "(μ-Alkoxo\diiron(II,II) Complexes of Tetrakis(2-(6-methylpyridyl)methyl)-1,3-diaminopropane-2-olate and Reversible Formation of O_2-adducts" Chem.Lett. 1992. 91-94 (1992)

[Publications] S.Patnaik: "A Structural Study on AgI-Ag_2O-CrO_3" J.Phys.Soc.Jpn.62. 536-543 (1992)

[Publications] Masahiro EBIHARA: "Synthesis,Structure,and Properties of Oxidized Hexamolybodenum Clusters" Inorg.Chem.31. 1645-1649 (1992)

[Publications] Michiko SATO: "Anion Sensing Electrodes Based on Nickel(II) Mixed Ligand Complexes" Chem.Lett.1992. 399-402 (1992)

[Publications] MAsayuki KOIKAWA: "Synthesis and Characterization of Fe(III) and Fe(IV) Complexes of N-(o-Hydroxyphenyl)salicylamide and Homologs" Inorg. Chim.Acta. 194. 75-80 (1992)

[Publications] Kenji SHINDO: "A Manganese(III) Complex of 3,5-Bis((salicylidene-amino)methyl)pyrazole:Synthesis,Structure,and Properties" Inorg.Chem.31. 4987-4990 (1992)

[Publications] Masaaki OHBA: "Synthesis and Magnetisms of Oxamido-and Oxamato-bridged Nickel(II)-Copper(II) Complexes" Bull.Chem.Soc.Jpn.65. 1988-1989 (1992)

[Publications] Megumu MUNAKATA: "Synthesis,Structures and Formation Constants of Cu(I) Complexes with Alkynes and 1,10-Phenanthroline" J.Chem.Soc.,Dalton Trans.1992. 2225-2230 (1992)

[Publications] Manabu NAKAHANADA: "Synthesis and Characterization of L-Tartrato Chromate(III) Complexes with Acetylacetonate Ions" J.Chem.Soc.,Dalton Trans.1992. 3423-3426 (1992)

[Publications] Yuzo NISHIDA: "Reaction Between Binuclear Iron(III) Compounds and DMPO (5,5-Dimethy1-3,5-dihydropyrrole N-Oxide)" J.Chem.Soc.,Chem.Commun. 1992. 93-94 (1992)

[Publications] Masaaki HAGA: "Photoexcited States of Biruthenium(II) Compounds Bridged by 2,2'-Bis(2-pyridyl)bibenzimidazole" Inorg.Chem.31. 548-555 (1992)

[Publications] Takashi MIYAMOTO: "Stability and Reactivity of Dihydroxobis(trimethy1-phosphine)platinum(II),an Intermediate Species for the Synthesis of Water-Soluble Phosphine Complexes" Bull.Chem.Soc.Jpn.65. 3386-3397 (1992)

[Publications] Koshiro TORIUMI: "Phase Transitions of the Halogen-Bridged M^<II>-X-M^<IV> Mixed-Valence Complexes[M(en)_2][MX_2(en)_2](ClO_4)_2" Acta Crystallogr.1992. (1992)

大川尚士九州大学, 理学部, 教授 (00037219)