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d-f遷移金属混合型錯体による新反応場の構築

研究報告コード R070000035
整理番号 R070000035
掲載日 2008年4月11日
研究者
  • 候 召民
研究者所属機関
  • 独立行政法人理化学研究所中央研究所侯有機金属化学研究室
研究機関
  • 独立行政法人理化学研究所中央研究所侯有機金属化学研究室
報告名称 d-f遷移金属混合型錯体による新反応場の構築
報告概要 新しい触媒の開発は、医薬品や高分子などの現代社会の成立に不可欠な有機物質を効率よく合成する手法の飛躍的進歩に繋がるだけでなく、新規機能性材料の創出にも繋がりうるなど様々な分野へ波及効果を持つ重要な研究課題である。高性能な新規触媒を開発するためには、各種金属の特性を最大限に活用し、斬新な分子設計に基づく新反応場の構築が極めて重要である。これまでは特に周期表の4族以降に位置する遷移金属を活性中心とする有機金属錯体触媒が活発に研究されてきたが、3族に属する希土類金属の錯体を触媒として利用する研究は少数に留まっていた。本課題ではそれら従来の遷移金属錯体とは異なる性質を持つと期待される希土類金属錯体を用いる触媒反応場の構築、特に複数の金属核が協奏的に作用する新しい多核構造を持つ希土類錯体触媒や、希土類を性質の異なる他の遷移金属錯体と結び付けた錯体触媒(d-f遷移金属混合型錯体)の開発、さらに、それらの新しい触媒を用いた新しい物質変換反応の開発を目標とし、研究を進めてきた
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研究分野
  • 遷移金属錯体一般
  • 重合触媒,重合開始剤
  • 触媒
関連発表論文 (1) "Tetranuclear Rare Earth Metal Polyhydrido Complexes Composed of "(C5Me4SiMe3)LnH2" Units. Unique Reactivities Toward Unsaturated C-C, C-N,and C-O Bonds", Cui, D.; Tardif, O.; Hou, Z. J. Am. Chem. Soc. 2004, 126, 1312-1313.
(2) "Hydrogenation of Carbon Dioxide and Aryl Isocyanates by a Tetranuclear Tetrahydrido Yttrium Complex. Isolation, Structures, and CO2 Insertion Reactions of Methylene Diolate and μ3-Oxo Yttrium Complexes", Tardif, O.; Hashizume, D.; Hou, Z. J. Am. Chem. Soc. 2004, 126, 8080-8081.
(3) "Scandium Half-Metallocene-Catalyzed Syndiospecific Styrene Polymerization and Styrene-Ethylene Copolymerization: Unprecedented Incorporation of Syndiotactic Styrene-Styrene Sequences in Styrene Ethylene Copolymers", Luo, Y.; Baldamus, J.; Hou, Z. J. Am. Chem. Soc. 2004, 126, 13910-13911.
(4) "A Novel Binuclear Samarium(II) Complex Bearing Mixed Cyclopentadienide/Siloxide Ligands: [(C5Me5)Sm{μ-OSi(OtBu)3}3Sm]. Synthesis , Structure, Electron-Transfer, and Unusual Metal Coordination Reactions", Nishiura, M.; Hou, Z.; Wakatsuki, Y. Organometallics 2004, 23, 1359- 1368.
(5) "Unprecedented Isospecific 3,4-Polymerization of Isoprene by Cationic Rare Earth Metal Alkyl Species Resulting from a Binuclear Precursor", Zhang, L.; Luo, Y.: Hou, Z. J. Am. Chem. Soc. 2005, 127, 14562-14563.
(6) "Catalytic Addition of Terminal Alkynes to Carbodiimides by Half Sandwich Rare Earth Metal Complexes", Zhang, W.; Nishiura, M.; Hou, Z. J. Am. Chem. Soc. 2005, 127, 16788 16789.
(7) "Alternating Copolymerization of Cyclohexene Oxide and Carbon Dioxide Catalyzed by Organo Rare Earth Metal Complexes", Cui, D.; Nishiura, M.; Hou, Z. Macromolecules 2005, 38, 4089-4095.
(8) "Scandium-Catalyzed Copolymerization of Ethylene with Dicyclopentadiene and Terpolymerization of Ethylene, Dicyclopentadiene, and Styrene", Li, X.; Hou, Z. Macromolecules 2005, 38, 6767-6769.
(9) "DFT Study of the Tetranuclear Lntetium and Yttrium Polyhydride Cluster Complexes [(C5Me4SiMe3)4Ln4H8] (Ln = Lu, Y) that Contain a Four-Coordinate Hydrogen Atom", Luo, Y.; Baldamus, J.; Tardif, O.; Hou, Z. Organometallics 2005, 24, 4362-4366.
(10) "Lanthanide-Imido Complexes and their Reactions with Benzonitrile", Cui, D.; Nishiura, M.; Hou, Z. Angew. Chem., Int. Ed., 2005, 44, 959-962.
(11) "Alternating Ethylene-Norbornene Copolymerization Catalyzed by Cationic Half-Sandwich Scandium Complexes", Li, X.; Baldamus, J.; Hou, Z. Angew. Chem., Int. Ed., 2005, 44, 962-965.
(12) "Hydrogenation of Carbon Monoxide by Tetranuclear Rare Earth Metal Polyhydrido Complexes. Selective Formation of Ethylene and Isolation of Well-Defined Polyoxo Rare Earth Metal Clusters", Shima, T.; Hou, Z. J. Am. Chem. Soc. 2006, 128, 8124-8125.
(13) "Catalytic Addition of Secondary Amines to Carbodiimides by a Half-Sandwich Yttrium Complex: An Efficient Route to N,N' ,N",N"-Tetra-substituted Guanidines", Zhang, W.; Nishiura, M.; Hou, Z. Synlett 2006, 1213-1216.
(14) "Cationic Polyhydrido Rare Earth Metal Complexes. Synthesis, Structure, and Catalysis in 1,3-Cyclohexadiene Polymerization", Li, X.; Baldamus, J.; Nishiura, M.; Tardif, O.; Hou, Z. Angew. Chem. Int. Ed. 2006, 45, 8184-8188.
(15) "Rare Earth Metal Bis(alkyl) Complexes Bearing a Monodentate Arylamido Ancillary Ligand. Synthesis, Structure, and Olefin Polymerization Catalysrs", Luo, Y.; Nishiura, M.; Hou, Z. J. Organomet. Chem. In press.
(16) "Modeling η5-C5Me4SiMe3 with η3-C3H5 for DFT study of a tetranuclear yttrium polyhydrido complex [(η5-C5Me4SiMe3)YH2]4", Luo, Y.; Hou, Z. Int. J. Quantum Chem. in press.
(17) "A Five-Center Rather than a Four-Center Transition State for Alkene Insertion into the Metal-Alkyl Bond of a Cationic Binuclear Yttrium Complex", Luo, Y.; Hou, Z. Organometallis in press.
(18) "Catalytic Addition of Amine N-H Bonds to Carbodiimides by Half-Sandwich Rare Earth Metal Complexcs: Efficient Synthesis of Substituted Guanidines through Amine Protonolysis of Rare Earth Metal Guanidinates", Zhang, W.; Nishiura, M.; Hou, Z. Chem. Eur. J. in press.
(19) "Cationic Rare Earth Metal Alkyls bearing a Bis-(phosphinophenyl)amido (PNP) Ancillary Ligand. An Excellent Catalyst System for Living cis-1,4-Polymerization and Copolymerization of Isoprene and Butadiene", Zhang, L.; Suzuki, T.; Luo, Y.; Nishiura, M.; Hou, Z. Angew. Chem. int. Ed. in press.
(20)「希土類ポリヒドリドクラスターの化学」、侯 召民、分子研研究会、2004年3月、岡崎
(21)「希土類金属ヒドリドクラスターの合成と特異な反応性」、侯 召民、第21回無機・分析化学コロキウム、2004年6月、蔵王
(22) "Rare Earth Metal Polyhydrido Complexes. Synthesis, Structures, and Novel Reactivity", Hou, Z. 21st International Conference on Organometallic Chemistry, 2004, July, Vancouver, Canada.
(23) "Catalytic and Stoichiometric Tranformations by Multimetallic Rare Earth Metal Complexes", Hou, Z. Rare Earths'04 in Nara JAPAN, 2004. November, Nara, Japan.
(24) "Cationic Rare Earth Metal Half-Sandwich Comploxes: A New Class of Olefin Polymerization Catalysts", Hou, Z. 8th International Symposium for Chinese Organic Chemists, ISCOC-8, 2004, December, Hong Kong, China.
(25)「希土類重合触媒の新展開」、侯 召民、21世紀COE「京都大学科学連携研究教育拠点」化学研究所第2回有機元素化学セミナー、2005年3月、宇治
(26) "Recent Progress in Organolanthanide Catalysis", Hou, Z. 24th Rare Earth Research Conference, 2005, June, Keystone, USA.
(27) "Cationic Half-Sandwich Rare Earth Metal Alkyls as Novel Cataiysts for Olefin Polymerization and Copolymerization", Hou, Z. The International Symposium on Dynamic Complexes (ISDC 2005), 2005, October, Sendai, Japan.
(28) "Organo Rare Earth Metal Catalysts for Olefin Polymerization and Copolymerization", Hou, Z. 1st Asian Polyolefin Workshop (APO 2005) 2005, December, Nara, Japan.
(29) "Lanthanide Hydride Clusters and Their Derivatives", Hou, Z. International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2005), 2005, December, Honolulu, USA,
(30) "Recent Developments in Organolanthanide Polymerization Catalysts", Hou, Z. International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2005), 2005, December, Honolulu, USA.
(31) "Novel Cross-Coupling Reactions of Terminal Alkynes or Anilines with Carbodiimides Catalyzed by Organolanthanide Complexes", Hou, Z. International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2005), 2005, December, Honolulu, USA.
(32) "Novel Olefin Polymerization Catalysts Based on Cationic Rare Earth Metal Alkyls", Hou, Z. international Symposium on Polymer Chemistry (PC 2006), 2006, June,Dalian,China.
(33) "Stereospecific Polymerization and Copolymerization of Acyelic and Cyelic Olefins by Group 3 Metal Catalysts", Hou, z., 41th International Symposium on Macromolecules (MACRO 2006), 2006,July, Rio de janeiro, Brazil.
(34)「希土類錯体の特長を生かした精密重合触媒の創製」、日本希土類学会第24回講演会、2006年11月、大阪
研究制度
  • 戦略的創造研究推進事業 さきがけタイプ(旧若手個人研究推進事業を含む)/合成と制御
研究報告資料
  • 候 召民. d-f遷移金属混合型錯体による新反応場の構築. さきがけプログラム「合成と制御」領域 Ⅲ期研究者・研究報告書(研究期間2003-2006年), 2007. p.5 - 21.

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