Formation of the concerted reaction field of sulfur skeletal poly-pyridine metal complex and its catalytic activity

• Project/Area Number: 18350033
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Osaka City University
• Principal Investigator: KINOSHITA Isamu Osaka City University, 大学院・理学研究科, 教授 (80128735)
• Co-Investigator(Kenkyū-buntansha): NISHIOKA Takanori 大阪市立大学, 大学院・理学研究科, 准教授 (10275240) ; 田中 里佳 大阪市立大学, 事務局, 技術職員 (80433316)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥16,330,000 (Direct Cost: ¥14,200,000、Indirect Cost: ¥2,130,000); Fiscal Year 2008: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2007: ¥5,330,000 (Direct Cost: ¥4,100,000、Indirect Cost: ¥1,230,000); Fiscal Year 2006: ¥7,100,000 (Direct Cost: ¥7,100,000)
• Keywords: カルバニオン / トリスチオレート / 有機銅 / ポリピリジン錯体 / 大環状ピリジン / トリスピリジルチオメタン / 銅 / 鉄 / ニッケル / カルベン / 金属錯体化学 / 有機金属化学 / 銅錯体 / ニッケル錯体 / トリポッド配位子 / 亜鉛錯体 / 人工光合成 / カリックスピリジン / ロジウム / ヤーンテラー効果

Research Abstract

硫黄骨格の大環状ピリジン配位子、チアカリックス[n]ピリジン(n=3, 4, 6 ; Py_3S_3, Py_4S_4, 及びPy_6S_6)ならびにトリポッド配位子、トリスピリジルチオメタン(tptmH)を開発し、第一遷移金属錯体群の特異的性質を明らかにした。Py_3S_3配位子は低酸化状態を安定化し、銅錯体は空気中で、有用なオレフィンのアジリジン化反応の触媒となる。一方トリスピリジルチオメタン(tptmH)配位子前駆体は[CuIIICl(tptm)]^+となり初めての三角両錘型Cu^(III)錯体を合成した。

Research Products

• [Journal Article] Compressed'Icelike Structures between Molecular Films Comparable with Ice Phase III. (2009)
  • Author(s): Yuki Yoshida, Riichi Miyamoto, Takanori Nishioka, Hideki Hashimoto, Isamu Kinoshita
  • Journal Title: Chem. Lett. 38 Pages: 366-367
  • Peer Reviewed
• [Journal Article] “Compressed"Icelike Structures between Molecular Films Comparable with Ice Phase III (2009)
  • Author(s): Yuki Yoshida
  • Journal Title: Chemistry Letters 38 Pages: 366-367
  • Peer Reviewed
• [Journal Article] Feasible attachment of dinuclear ruthenium complex to gold electrode surface via new ligand substitution reaction. (2009)
  • Author(s): Hideaki Takagi
  • Journal Title: Electrochimica Acta 54 Pages: 1286-1291
  • Peer Reviewed
• [Journal Article] Ruthenium and Rhodium Complexes with Thiolate-Containing Pincer Ligands Produced by C-S Bond Cleavage of Pyridyl-Substituted Dibenzothiophenes (2008)
  • Author(s): Mayuko Shibue, Masakazu Hirotsu, Takanori Nishioka, Isamu Kinoshita
  • Journal Title: Organometallics 27 Pages: 4475-4483
  • Peer Reviewed
• [Journal Article] A Thiacalix[3]pyridine Copper(I) Complex as a Highly Active Catalyst for the Olefin Aziridination Reaction (2008)
  • Author(s): Yuhei Tsukahara, Masakazu Hirotsu, Shin-ichi Hattori, Yoshinosuke Usuki, and Isamu Kinoshita
  • Journal Title: Chem. Lett. (4), 37 Pages: 452-453
  • NAID: 10021079750
  • Peer Reviewed
• [Journal Article] Synthesis and characterization of tris(2-pyridylthio)methanido Zn complex with a Zn-C bond and DFT calculation of its one-electron oxidized species (2008)
  • Author(s): Ken'ichi Kitano, Naoto Kuwamura, Rika Tanaka, Ryoko Santo, Takanori Nishioka, Akio Ichimura and Isamu Kinoshita
  • Journal Title: Chem. Commun Pages: 1314-1316
  • Peer Reviewed
• [Journal Article] Mimicking the Photosynthetic system with Strong Hydrogen Bonds to Promote Proton Electron Concerted Reactions' (2008)
  • Author(s): I.Kinoshita, H.Hashimoto, T.Nishioka, R.Miyamoto, N.Kuwamura, and Y.Yoshida
  • Journal Title: Photosyn. Res. 95 Pages: 363-378
  • Peer Reviewed
• [Journal Article] Ruthenium and Rhodium Complexes with Thiolate-Containing Pincer Ligands Produced by C-S Bond Cleavage of Pyridyl-Substituted Dibenzothiophenes. (2008)
  • Author(s): Shibue, Mayuko
  • Journal Title: Organometallics 27 Pages: 4475-4483
  • Peer Reviewed
• [Journal Article] Syntheses, structural characterization and photophysical properties of 4-(2-pyridyl)-l, 2, 3-triazole rhenium(I)complexes. (2008)
  • Author(s): Obata, Makoto
  • Journal Title: Dalton Transactions 2008 Pages: 3292-3300
  • Peer Reviewed
• [Journal Article] A Thiacalix[3]pyridine Copper(I)Complex as a Highly Active Catalyst for the Olefin Aziridination Reaction (2008)
  • Author(s): 塚原 侑平
  • Journal Title: Chem.Lett. 37 Pages: 452-453
  • Peer Reviewed
• [Journal Article] Synthesis and characterization of tris(2-pyridylthio)methanido Zn complex with a Zn-C bond and DFT calculation of its one-electron oxidized species (2008)
  • Author(s): 北野 健一
  • Journal Title: Chem.Commun. Pages: 1314-1316
  • Peer Reviewed
• [Journal Article] Structure and dynamic properties of substituted carbonylhydride clusters H2RuOs3(CO)13 and H4Ru4(CO)12 containing functionalized phoshines (2008)
  • Author(s): I.A.Andreev
  • Journal Title: Russian Chemical Bulletin, Internationa Edition 56 Pages: 1343-1350
  • Peer Reviewed
• [Journal Article] Syntheses,structural characterization and photophysical properties of 4-(2-pyridyl)-1,2,3-triazole rhenium(l)complexes (2008)
  • Author(s): 小幡 誠
  • Journal Title: Photosyn.Res. (In press)
  • Peer Reviewed
• [Journal Article] Sugar-Incorpolated N-Heterocyclic Carbene Complexes (2007)
  • Author(s): Takanori Nishioka, Teppei Shibata, Isamu Kinoshita
  • Journal Title: Organometallics 26 Pages: 1126-1128
  • Peer Reviewed
• [Journal Article] Sugar-Incorporated N-Heterocyclic Carbene Complexes (2007)
  • Author(s): 西岡孝訓
  • Journal Title: Organometallics 26
• [Journal Article] Structure-Activity Relationship of Insulinomimetic Activity of Zinc(II) Complexes with Pyridine-2-sulfonic Acid Derivatives (2007)
  • Author(s): 吉川 豊
  • Journal Title: Bull. Chem. Soc. Jpn 80
• [Journal Article] Conformational Conversion of Copper Complexes Title : Observation of Halide Induced Conformational Conversion of Dinuclear Copper Complexes Having a Tetradentate Polypyridine Ligand with a p-Xylene Backbone (2007)
  • Author(s): 西岡 孝訓
  • Journal Title: Bull. Chem. Soc. Jpn 80(In press)
• [Journal Article] Diamagnetic-paramagnetic conversion of tris(2-pyridylthio)methylcopper(III) through a structural change from trigonal bipyramidal to octahedral (2006)
  • Author(s): Santo, Ryoko ; Miyamoto, Riichi ; Tanaka, Rika ; Nishioka, Takanori ; Sato, Kazunobu ; Toyota, Kazuo ; Obata, Makoto ; Yano, Shigenobu ; Kinoshita, Isamu ; Ichimura, Akio ; Takui, Takeji
  • Journal Title: Angew. Chem. Int. ed. 45 Pages: 7611-7614
  • Peer Reviewed
• [Journal Article] Thiacalix[3]pyridine produces a stable mononuclear rhodium(II) complex with mutual Jahn-Teller effect (2006)
  • Author(s): Rika Tanaka Hamazawa, Takanori Nishioka, Isamu Kinoshita, Takeji Takui, Ryoko Santo and Akio Ichimura
  • Journal Title: Dalton Trans Pages: 1374-1376
  • Peer Reviewed
• [Journal Article] Diamagnetic-paramagnetic conversion of tris(2-pyridylthio)methylcopper(III) through a structural change from trigonal bipyramidal to octahedral. (2006)
  • Author(s): 山東 良子
  • Journal Title: AngeWandte Chemie Int. ed. Engl 45
• [Journal Article] Thiacalix[3]pyridine produces a stable mononuclear rhodium(II) complex with mutual Jahn-Teller effect (2006)
  • Author(s): 田中 里佳
  • Journal Title: Dalton Transaction 2006
• [Presentation] ジチオカルペンを有するNCNピンサー型鉄錯体の合成と電子構造 (2009)
  • Author(s): 加藤 諒
  • Organizer: 日本化学会春季年会
  • Place of Presentation: 日大舟橋
  • Year and Date: 2009-03-28
• [Presentation] Cu-C(sp^3)結合を持つトリポット型銅(II)及び銅(III)錯体の配位子酸化挙動 (2008)
  • Author(s): 大井秀隆
  • Organizer: 第41回酸化討論会
  • Place of Presentation: 九州大学
  • Year and Date: 2008-11-28
• [Presentation] Electrochemical Properties of Multinuclear Carbonato Complexes (2008)
  • Author(s): Naoto Kuwamura, Ken'ichi Kitano, Riichi Miyamoto, Yuki Yoshida, Masakazu Hirotsu, Takanori Nishioka, Akio Ichimura, and Isamu Kinoshita
  • Organizer: 15th International SPACC Symposium
  • Place of Presentation: Osaka, Japan
  • Year and Date: 2008-11-20
• [Presentation] Diastereoselective Syntheses of"Sugar-Coated" N-Heterocyclic CarbeneIr(III)Complexes (2008)
  • Author(s): Shibata, Teppei
  • Organizer: International symposium on Pure and Applied Coordination Chemistry (16^<th> SPACC Symposium)
  • Place of Presentation: 大阪市ホテルメトロ
  • Year and Date: 2008-11-20
• [Presentation] Coordination Ability of a Thiacalix[3]pyridine Copper Unit toward Olefins (2008)
  • Author(s): Nishikawa, Yusuke
  • Organizer: (16^<th> SPACC Symposium)
  • Place of Presentation: 大阪市ホテルメトロ
  • Year and Date: 2008-11-20
• [Presentation] Synthesis of Ruthenium Complexes of N, S-Bidentate Ligands (2008)
  • Author(s): Yogi, Akira
  • Organizer: (16^<th> SPACC Symposium)
  • Place of Presentation: 大阪市ホテルメトロ
  • Year and Date: 2008-11-20
• [Presentation] Ligand Oxidation Behavior on the Tripodal Cu(II/III)Complex Containinga Cu-C(sp3)Bond (2008)
  • Author(s): Ohi, Hidetaka
  • Organizer: (16^<th> SPACC Symposium)
  • Place of Presentation: 大阪市ホテルメトロ
  • Year and Date: 2008-11-20
• [Presentation] Reactivity of Pyridyl-Substituted Dibenzothiophenes toward Transition Metal Carbonyls (2008)
  • Author(s): Tsuboi, Chiaki
  • Organizer: (16^<th> SPACC Symposium)
  • Place of Presentation: 大阪市ホテルメトロ
  • Year and Date: 2008-11-20
• [Presentation] Syntheses of Copper Complexes with Sugar Incorporated Sulfur-Bridged Polypyridine Ligands (2008)
  • Author(s): Takeguchi, Katsuya
  • Organizer: (16^<th> SPACC Symposium)
  • Place of Presentation: 大阪市ホテルメトロ
  • Year and Date: 2008-11-20
• [Presentation] Structures of Two- and Three-Dimensional Cu(I, II)Mixed-Valence Coordination Polymers (2008)
  • Author(s): Yoshida, Yuki
  • Organizer: (16^<th> SPACC Symposium)
  • Place of Presentation: 大阪市ホテルメトロ
  • Year and Date: 2008-11-20
• [Presentation] Organic Reactions on Metal Complexes with Tripodal Carbanion Ligands (2008)
  • Author(s): Ohi, Hidekazu
  • Organizer: 有機金属討論会2008
  • Place of Presentation: 大阪府立大学
  • Year and Date: 2008-09-28
• [Presentation] Chelate Type Picolyl"sugar Coated" N-Heterocyclic Carbene Complex (2008)
  • Author(s): Shibata, Teppei
  • Organizer: 有機金属討論会2008
  • Place of Presentation: 大阪府立大学
  • Year and Date: 2008-09-28
• [Presentation] Cu-C(sp3)結合を持つ銅二核錯体の合成と性質 (2008)
  • Author(s): 吉田佑希
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢大学
  • Year and Date: 2008-09-20
• [Presentation] C-H活性化を伴うトリポット型銅錯体の合成 (2008)
  • Author(s): 大井秀隆
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢大学
  • Year and Date: 2008-09-20
• [Presentation] 糖修飾N一複素環カルペンイリジウム錯体の合成と構造 (2008)
  • Author(s): 柴田鉄平
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢大学
  • Year and Date: 2008-09-20
• [Presentation] C-Cu-Fを軸とする三方両錘型銅(III)錯体の性質 (2008)
  • Author(s): 加藤 諒
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢大学
  • Year and Date: 2008-09-20
• [Presentation] The Interaction of Macrocyclic Ag and Cu Complexes with Carotenoid (2008)
  • Author(s): Kinoshita, Isamu
  • Organizer: The I5th International Symposium on Carotenoids
  • Place of Presentation: Okinawa Moon Beach Hotel
  • Year and Date: 2008-07-24
• [Presentation] C-H活性化を伴うトリポッド型銅錯体の合成 (2008)
  • Author(s): 大井秀隆、桑村直人、品田哲郎、大船泰史、廣津昌和、西岡孝訓、木下勇
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢大学
• [Presentation] 不斉源を持つ三脚型有機銅(II)錯体の合成 (2008)
  • Author(s): 大井 秀隆
  • Organizer: 日本化学会第88春期年会1E5-37
  • Place of Presentation: 立教大学池袋キャンパス
• [Presentation] ジベンゾチオフェン誘導体を用いたロジウム錯体の合成 (2008)
  • Author(s): 廣津 昌和
  • Organizer: 日本化学会第88春季年会4E8-52
  • Place of Presentation: 立教大学池袋キャンパス
• [Presentation] The oligo(pyridylthio)system for probing the suspicious oxidat ion states for metal ions (2007)
  • Author(s): I.Kinoshita
  • Organizer: 14^<th> International SPACC-CSJ Symposium AL2
  • Place of Presentation: National Taipei University,Taipei,Taiwan
  • Year and Date: 2007-12-23
• [Presentation] Synthetic strategy of rare oxidation state complexes for copper and rhodium〔28^<th>〕International Conference on Science and Technolog (2007)
  • Author(s): Isamu Kinoshita
  • Organizer: [28^<th>]International Conference on Science and Technolog
  • Place of Presentation: Praha Czech
  • Year and Date: 2007-07-05
• [Presentation] カルバニオンが配位する二核ニッケル(II)錯体の電極反応解析 (2007)
  • Author(s): 桑村直人・北野健一・西岡孝訓・木下勇・市村彰男
  • Organizer: 第57回錯体化学討論会
  • Place of Presentation: 名古屋工業大学(名古屋市)、1C-05
• [Presentation] Cu(II)カルバニオン錯体によるプロトン電子協奏系の構築 (2007)
  • Author(s): 木下勇
  • Organizer: 日本化学会第87春期年会
  • Place of Presentation: 関西大学千里山キャンパス(吹田市)、1S3-05
• [Presentation] ジベンゾチオフェン含有配位子のC-S結合開裂によるS,C,N-三座配位ロジウム錯体の合成 (2007)
  • Author(s): 渋江 麻友子
  • Organizer: 第57回錯体化学討論会2Ab-16
  • Place of Presentation: 名古屋工業大学(名古屋市)
• [Presentation] 糖修飾N-ヘテロ環カルベンニッケル錯体の合成 (2007)
  • Author(s): 西岡 孝訓
  • Organizer: 第57回錯体化学討論会2Ab-07
  • Place of Presentation: 名古屋工業大学(名古屋市)
• [Presentation] カルバニオンが配位する二核ニッケル(II)錯体の電極反応解析 (2007)
  • Author(s): 桑村 直人
  • Organizer: 第57回錯体化学討論会1C-05
  • Place of Presentation: 名古屋工業大学(名古屋市)
• [Presentation] カルバニオンが配位した三方両錘型銅(III)錯体の合成と反応 (2006)
  • Author(s): 山東良子・宮本利一・木下勇・市村彰男
  • Organizer: 第56回錯体化学討論会
  • Place of Presentation: 広島大学東千田キャンパス(広島市)、2Ab07
• [Presentation] 稀な酸化状態を持つ金属錯体の合成戦略 (2006)
  • Author(s): 木下勇
  • Organizer: 第56回錯体化学討論会
  • Place of Presentation: 広島大学東千田キャンパス(広島市)、2S5
• [Remarks]
  • URL: http://www.materials.sci.osaka-cu.ac.jp/SEKKEI./index.htm