Synthesis of Cationic Transition Metal Complexes and Their Application to Transformation of Carbon Dioxide

• Project/Area Number: 20350031
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: The Institute of Physical and Chemical Research
• Principal Investigator: MATSUO Tsukasa The Institute of Physical and Chemical Research, 機能性有機元素化学特別研究ユニット, 副ユニットリーダー (90312800)
• Project Period (FY): 2008 – 2010
• Project Status: Completed (Fiscal Year 2010)
• Budget Amount: ¥18,980,000 (Direct Cost: ¥14,600,000、Indirect Cost: ¥4,380,000); Fiscal Year 2010: ¥6,110,000 (Direct Cost: ¥4,700,000、Indirect Cost: ¥1,410,000); Fiscal Year 2009: ¥6,110,000 (Direct Cost: ¥4,700,000、Indirect Cost: ¥1,410,000); Fiscal Year 2008: ¥6,760,000 (Direct Cost: ¥5,200,000、Indirect Cost: ¥1,560,000)
• Keywords: 二酸化炭素 / メタン / ヒドロシラン / シロキサン / 均一系触媒 / ジルコニウム / カチオン性錯体 / アリールオキシド配位子 / チオラート配位子 / アニリド配位子 / 還元 / 鉄 / ヒドリド錯体 / アミド配位子 / パラキノン

Research Abstract

Transition metal complexes have been synthesized by using a newly developed bulky monodentate aryloxide ligand based on a rigid fused-ring s-hydrindacenyl skeleton. Their molecular structures have been confirmed by X-ray crystallography. The new cationic zirconium complexes showed an improved catalytic ability for hydrosilylation of carbon dioxide, comparing with those of the previously reported catalysts having multidentate ligands. Theoretical calculations were performed to examine the reaction mechanism for the chemical reduction of carbon dioxide. Also olefin polymerization reactions have been studied with the use of cationic transition complexes.

Research Products

• [Journal Article] Coordination Chemistry and Organic Synthesis Utilizing Cycloalkane-1,2-dithiol (2011)
  • Author(s): Akihiko Ishii, Tomoyuki Toda, Norio Nakata, Tsukasa Matsuo
  • Journal Title: Phosphorus, Sulfur and Silicon and the Related Elements (in press)
  • Peer Reviewed
• [Journal Article] Air- and Moisture-Stable p-Monothiobenzoquinones Incorporated in an Octaalkyl-s-hydrindacene Skeleton (2011)
  • Author(s): Makoto Hachiya, Mikinao Ito, Tsukasa Matsuo, Daisuke Hashizume, Hiroyuki Fueno, Kazuyoshi Tanaka, Kohei Tamao
  • Journal Title: Org.Lett. 13 Pages: 2666-2669
  • Peer Reviewed
• [Journal Article] Synthesis and structures of dialkyl zirconium complexes with an [OSSO]-type bis(phenolate) ligand bearing a trans-1,2-cyclooctanediylbis(thio) unit (2011)
  • Author(s): Tomoyuki Toda, Norio Nakata, Tsukasa Matsuo, Akihiko Ishii
  • Journal Title: J.Organomet.Chem. 696 Pages: 1258-1261
  • Peer Reviewed
• [Journal Article] Synthesis and reactivity of niobium complexes having a tripodal triaryloxide ligand in bidentate, tridentate, and tetradentate coordination modes (2011)
  • Author(s): Fumio Akagi, Yutaka Ishida, Tsukasa Matsuo, Hiroyuki Kawaguchi
  • Journal Title: Dalton Trans. 40 Pages: 2375-2382
  • Peer Reviewed
• [Journal Article] Synthesis and structures of dialkyl zirconium complexes with an [OSSO]-type bis(phenolate) ligand bearing a trans-1,2-cyclooctanediylbis(thio) unit (2011)
  • Author(s): T.Toda, 他3名
  • Journal Title: Journal of Organometallic Chemistry Volume: (印刷中)
  • Peer Reviewed
• [Journal Article] Synthesis and reactivity of niobium complexes having a tripodal triaryloxide ligand in bidentate, tridentate, and teradentate coordination modes (2011)
  • Author(s): F.Akagi, 他3名
  • Journal Title: Dalton Transactions Volume: 40 Pages: 2375-2382
  • Peer Reviewed
• [Journal Article] Syntheses and structures of zirconium(IV) complexes supported by 2,6-di-adamantyl-aryloxide ligands and formation of arene-bridged dizirconium complexes with an inverse sandwich structure (2010)
  • Author(s): Takahito Watanabe, Yutaka Ishida, Tsukasa Matsuo, Hiroyuki Kawaguchi
  • Journal Title: Dalton Trans. 39 Pages: 484-491
  • Peer Reviewed
• [Journal Article] Syntheses and structures of zirconium(IV)complexes supported by 2,6-diadamantylaryloxide ligands and formation of arene-bridged dizirconium complexes with an inverse sandwich structure (2010)
  • Author(s): T.Watanabe, 他3名
  • Journal Title: Dalton Transactions 39 Pages: 484-491
  • Peer Reviewed
• [Journal Article] Isolated Monomeric and Dimeric Mixed Diorganocuprates Based on the Size-Controllable Bulky "Rind" Ligands (2009)
  • Author(s): Mikinao Ito, Daisuke Hashizume, Takeo Fukunaga, Tsukasa Matsuo, Kohei Tamao
  • Journal Title: J.Am.Chem.Soc. 131 Pages: 18024-18025
  • Peer Reviewed
• [Journal Article] Zirconium Complex of an [OSSO]-Type Diphenolate Ligand Bearing trans-1,2-Cyclooctane- diylbis(thio) Core : Synthesis, Structure, and Isospecific 1-Hexene Polymerization (2009)
  • Author(s): Akihiko Ishii, Tomoyuki Toda, Norio Nakata, Tsukasa Matsuo
  • Journal Title: J.Am.Chem.Soc. 131 Pages: 13566-13567
  • Peer Reviewed
• [Journal Article] DFT Study on N_2 Activation by a Hydride-Bridged Diniobium Complex. N≡N Bond Cleavage Accompanied by H_2 Evolution (2009)
  • Author(s): Hiromasa Tanaka, Yoshihito Shiota, Tsukasa Matsuo, Hiroyuki Kawaguchi, Kazunari Yoshizawa
  • Journal Title: Inorg.Chem. 48 Pages: 3875-3881
  • Peer Reviewed
• [Journal Article] Reductive Coupling of Six Carbon Monoxides by a Ditantalum Hydride Complex (2009)
  • Author(s): Takahito Watanabe, Yutaka Ishida, Tsukasa Matsuo, Hiroyuki Kawaguchi
  • Journal Title: J.Am.Chem.Soc. 131 Pages: 3474-3475
  • Peer Reviewed
• [Journal Article] DFT Study on N_2 Activation by a Hydride-Bridged Diniobium Complex. N=N Bond Cleavage Accompanied by H_2 Evolution (2009)
  • Author(s): H.Tanaka, 他5名
  • Journal Title: Inorganic Chemistry 48 Pages: 3857-3881
  • Peer Reviewed
• [Journal Article] Zirconium Complex of an[OSSO]-Type Diphenolate Ligand Bearing trans-1, 2- Cyclooctanediylbis(thio)Core : Synthesis, Structure, and Isospecific 1-Hexene Polymerization (2009)
  • Author(s): A.Ishii, 他3名
  • Journal Title: Journal of American Chemical Society 131 Pages: 13566-13567
  • Peer Reviewed
• [Journal Article] Isolated Monomeric and Dimeric Mixed Diorganocuprates Based on the Size-Controllable Bulky "Rind" Ligands (2009)
  • Author(s): M.Ito, 他4名
  • Journal Title: Journal of American Chemical Society 131 Pages: 18024-18025
  • Peer Reviewed
• [Journal Article] Reductive Coupling of Six Carbon Monoxide by a Ditantalum Hydride Complex (2009)
  • Author(s): T. Watanabe, 他3名
  • Journal Title: Journal of American Chemical Society 131(印刷中)
  • Peer Reviewed
• [Journal Article] 縮環型立体保護基によって安定化された高周期典型元素多重結合を含む新規π共役電子系の開発 (2009)
  • Author(s): T. Matsuo, 他1名
  • Journal Title: 月刊ファインケミカル 38 Pages: 66-84
• [Presentation] シクロオクタン環を有する[OSSO]型ビス(フェノラト)4族金属錯体を触媒とするオレフィン重合反応 (2011)
  • Author(s): 戸田智之、松尾司、他
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(横浜)
  • Year and Date: 2011-03-29
• [Presentation] 直線二配位Fe錯体の巨大内部磁場 (2011)
  • Author(s): 小林義男、松尾司、他
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(横浜)
  • Year and Date: 2011-03-27
• [Presentation] μSR Study of Linear Two-Coordinate Fe Complexes with Bulky Arylthiol Ligands (2010)
  • Author(s): 石井康之、松尾司、他
  • Organizer: Pacifichem 2010
  • Place of Presentation: ホノルル(ハワイ)
  • Year and Date: 2010-12-18
• [Presentation] Mossbauer Studies of Linear Two-Coordinate Fe Complexes with Bulky Arylthiol Ligands (2010)
  • Author(s): 小林義男、松尾司、他
  • Organizer: Pacifichem 2010
  • Place of Presentation: ホノルル(ハワイ)
  • Year and Date: 2010-12-18
• [Presentation] μSR Study of Linear Two-Coordinate Fe Complexes with Bulky Arylthiol Ligands (2010)
  • Author(s): Y.Ishii, 他6名
  • Organizer: Pacifichem 2010
  • Place of Presentation: ホノルル、ハワイ
  • Year and Date: 2010-12-18
• [Presentation] Mossbauer Studies of Linear Two-Coordinate Fe Complexes with Bulky Arylthiol Ligands (2010)
  • Author(s): Y.Kobayashi, 他7名
  • Organizer: Pacifichem 2010
  • Place of Presentation: ホノルル、ハワイ
  • Year and Date: 2010-12-18
• [Presentation] Isolation of Monomeric and Dimeric Organobromo-cuprates and Mixed Diorganocuprates Based on the Size-Controllable"Rind" Ligands and Their Oxidation Reactions (2010)
  • Author(s): 伊藤幹直、松尾司、他
  • Organizer: Pacifichem 2010
  • Place of Presentation: ホノルル(ハワイ)
  • Year and Date: 2010-12-16
• [Presentation] Synthesis of Bulky Para-Phenylene Type Di-functional Compounds Based on an s-Hydrindacene Skeleton (2010)
  • Author(s): 蜂屋誠、松尾司、他
  • Organizer: Pacifichem 2010
  • Place of Presentation: ホノルル(ハワイ)
  • Year and Date: 2010-12-16
• [Presentation] Isolation of Monomeric and Dimeric Organobromocuprates and Mixed Diorgano-cuprates Based on the Size-Controllable "Rind" Ligands and Their Oxidation Reactions (2010)
  • Author(s): M.Ito, 他3名
  • Organizer: Pacifichem 2010
  • Place of Presentation: ホノルル、ハワイ
  • Year and Date: 2010-12-16
• [Presentation] ヒドロインダセン骨格を用いたかさ高い単座配位子を有する直線型二配位鉄錯体の合成と性質 (2010)
  • Author(s): 伊藤幹直、松尾司、他
  • Organizer: 第60回錯体化学討論会
  • Place of Presentation: 大阪国際交流センター(大阪)
  • Year and Date: 2010-09-28
• [Presentation] シクロオクタン環を有する[OSSO]型配位子を用いた5族金属錯体の合成 (2010)
  • Author(s): 戸田智之、松尾司、他
  • Organizer: 第60回錯体化学討論会
  • Place of Presentation: 大阪国際交流センター(大阪)
  • Year and Date: 2010-09-28
• [Presentation] 新規な四座[OSSO]型配位子を有する4族金属錯体の合成とイソ選択的α-オレフィン重合 (2010)
  • Author(s): 中田憲男、松尾司、他
  • Organizer: 第57回有機金属化学討論会
  • Place of Presentation: 中央大学多摩キャンパス(八王子)
  • Year and Date: 2010-09-28
• [Presentation] Synthesis and α-Olefin Polymerization Activity of Zirconium Complex Incorporating A New Tetradentate [OSSO]-Type Ligand (2010)
  • Author(s): 中田憲男、松尾司、他
  • Organizer: 24th International Conference on Organometallic Chemistry
  • Place of Presentation: 台北(台湾)
  • Year and Date: 2010-07-22
• [Presentation] Synthesis and α-Olefin Polymerization Activity of Zirconium Complex Incorporating A New Tetradentate [OSSO]-Type Ligand (2010)
  • Author(s): N.Nakata, 他4名
  • Organizer: 24th International Conference on Organometallic Chemistry
  • Place of Presentation: Taipei, Taiwan
  • Year and Date: 2010-07-22
• [Presentation] Hafnium Complex with an [OSSO]-Type Diphenolate Ligand Bearing a Trans-1,2-cyclooctane Ring: Synthesis and Isospecific α-Olefin Polymerization (2010)
  • Author(s): 戸田智之、松尾司、他
  • Organizer: 24th International Conference on Organometallic Chemistry
  • Place of Presentation: 台北(台湾)
  • Year and Date: 2010-07-19
• [Presentation] Hafnium Complex with An [OSSO]-Type Diphenolate Ligand Bearing A Trans-1,2-cyclooctane Ring : Synthesis and Isospecific α-Olefin Polymerization (2010)
  • Author(s): T.Toda, 他4名
  • Organizer: 24th International Conference on Organometallic Chemistry
  • Place of Presentation: Taipei, Taiwan
  • Year and Date: 2010-07-19
• [Presentation] ヒドロインダセン骨格から成るかさ高いパラフェニレン型二官能性化合物の合成 (2010)
  • Author(s): 蜂屋誠、松尾司、他
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学(東大阪)
  • Year and Date: 2010-03-27
• [Presentation] trans-シクロオクタン環を有する[OSSO]型ビス(フェノラト)ハフニウム錯体:合成とアルケン重合 (2010)
  • Author(s): 戸田智之、松尾司、他
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学(東大阪)
  • Year and Date: 2010-03-27
• [Presentation] trans-シクロオクタン環を有する[OSSO]型ビス(フェノラト)バフニウム錯体:合成とアルケン重合 (2010)
  • Author(s): T.Toda, 他4名
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学(東大阪)
  • Year and Date: 2010-03-27
• [Presentation] 有機銅化合物の酸化によるかさ高いフェノール誘導体Rind-OHとその金属錯体の合成 (2010)
  • Author(s): 伊藤幹直、松尾司、他
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学(東大阪)
  • Year and Date: 2010-03-26
• [Presentation] Synthesis and Structural Characterization of Mixed Diorganocuprates Bearing Bulky "Rind" Groups (2009)
  • Author(s): 松尾司、他
  • Organizer: 新学術領域研究「高次π空間の創発と機能開発」第1回国際シンポジウム
  • Place of Presentation: ホテル阪急エキスポパーク(吹田)
  • Year and Date: 2009-12-18
• [Presentation] Synthesis and Structural Characterization of Mixed Diorganocuprates Bearing Bulky "Rind" Groups (2009)
  • Author(s): 伊藤幹直、松尾司、他
  • Organizer: 北海道大学触媒化学研究センター20周年記念国際シンポジウム
  • Place of Presentation: 北海道大学(札幌)
  • Year and Date: 2009-12-07
• [Presentation] かさ高い縮環型立体保護基を有する遷移金属チオラート錯体の合成と性質 (2009)
  • Author(s): 伊藤幹直、松尾司、他
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎大学(長崎)
  • Year and Date: 2009-09-26
• [Presentation] シクロオクタン縮環[OSSO]型配位子を有する4族金属錯体の合成とオレフィン重合反応への展開 (2009)
  • Author(s): 戸田智之、松尾司、他
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎大学(長崎)
  • Year and Date: 2009-09-25
• [Presentation] かさ高いRind基を有する有機銅化合物の合成とその性質 (2009)
  • Author(s): 伊藤幹直、松尾司、他
  • Organizer: 第56回有機金属化学討論会
  • Place of Presentation: 同志社大学(京都)
  • Year and Date: 2009-09-11
• [Presentation] 均一系触媒を用いた二酸化炭素の還元 (2009)
  • Author(s): 松尾司
  • Organizer: 第44回有機反応若手の会
  • Place of Presentation: 埼玉県立スポーツ研修センター(上尾)
  • Year and Date: 2009-07-09
• [Presentation] 均一系触媒を用いた二酸化炭素からメタンへの変換 (2009)
  • Author(s): 松尾司
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学(船橋)
  • Year and Date: 2009-03-28
• [Presentation] 縮環構造を有するかさ高いアリールオキシドおよびアリールチオラート配位子の開発と金属錯体の合成 (2008)
  • Author(s): 伊藤幹直、松尾司、他
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢大学(金沢)
  • Year and Date: 2008-09-21
• [Presentation] Homogeneous Reduction of Carbon Dioxide with Hydrosilanes Catalyzed by Zirconium-Borane Complexes (2008)
  • Author(s): 松尾司、他
  • Organizer: 15th International Symposium on Silicon Chemistry Post Symposium
  • Place of Presentation: ホテルメトロポリタン高崎(高崎)
  • Year and Date: 2008-06-10
• [Presentation] Homogeneous Reduction of Carbon Dioxide with Hydrosilanes Catalyzed by Zirconium-Borane Complexes (2008)
  • Author(s): T. Matsuo, 他2名
  • Organizer: ポストISOS XVシンポジウム
  • Place of Presentation: 高崎
  • Year and Date: 2008-06-10
• [Presentation] Homogeneous Reduction of Carbon Dioxide with Hydrosilanes Catalyzed by Zirconium-Borane Complexes (2008)
  • Author(s): 松尾司、他
  • Organizer: 15th International Symposium on Silicon Chemistry
  • Place of Presentation: 済州島(韓国)
  • Year and Date: 2008-06-03
• [Presentation] Homogeneous Reduction of Carbon Dioxide with Hydrosilanes Catalyzed by Zirconium-Borane Complexes (2008)
  • Author(s): T. Matsuo, 他2名
  • Organizer: 第15回有機ケイ素化学国際会議
  • Place of Presentation: 済州島
  • Year and Date: 2008-06-03
• [Book] 二酸化炭素の有効利用技術 (2010)
  • Author(s): 松尾司
  • Publisher: (株)サイエンス&テクノロジー
• [Book] 二酸化炭素の有効利用技術 (2010)
  • Author(s): 松尾司, 他多数
  • Total Pages: 370
  • Publisher: (株)サイエンス&テクノロジー
• [Remarks] ホームページ等
  • URL: http://www.asi.riken.jp/jp/laboratories/srunits/feoc/index.html