Development of molecular transformation reactions by use of cooperative effect of multinuclear rare earth metal complexes

• Project/Area Number: 19750053
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Inorganic chemistry
• Research Institution: The Institute of Physical and Chemical Research
• Principal Investigator: NISHIURA Masayoshi The Institute of Physical and Chemical Research, 侯有機金属化学研究室, 研究員 (30332258)
• Project Period (FY): 2007 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥3,090,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥390,000); Fiscal Year 2008: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2007: ¥1,400,000 (Direct Cost: ¥1,400,000)
• Keywords: 希土類アルキル錯体 / ピロリル配位子 / アセチリド錯体 / スチレン / イソシアニド / 末端アルキン / クロスカップリング反応 / 希土類 / フォスフォリル配位子 / アルキル錯体 / ヒドリド錯体 / 重合 / アニオン性錯体 / アジド

Research Abstract

ハーフサンドイッチ型アルキル錯体は、末端アルキンとイソシアニドとのZ選択的クロスカップリング反応に対して高い活性を示し、2つの金属の協同効果により高いZ選択性が発現することを明らかにした。中性の他に新たにアニオン性のポリヒドリド錯体の合成に成功し、トリメチルシリルアジドを用いて反応性を比較したところ、中性のヒドリド錯体ではSi-N結合の切断反応が起こり、アニオン性ヒドリド錯体ではN-N結合の切断がおこり、顕著な反応性の違いが見られた。

Research Products

• [Journal Article] Synthesis of (Z)-1-Aza-1,3-enynes by the Cross-Coupling of Terminal Alkynes with Isocyanides Catalyzed by Rare-Earth Metal Complexes (2008)
  • Author(s): W. Zhang, M. Nishiura, and Z. Hou
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 9700-9703
  • Peer Reviewed
• [Journal Article] Carboxylation of Organoboronic Esters Catalyzed by N-Heterocyclic Carbene Copper(I) Complexes (2008)
  • Author(s): T. Ohishi, M. Nishiura, and Z. Hou
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 5792-5795
  • Peer Reviewed
• [Journal Article] Cationic Scandium Allyl Complexes Bearing Mono(cyclopentadienyl) Ligands : Synthesis, Novel Structural Variety, and Olefin-Polymerization Catalysis (2008)
  • Author(s): N. Yu, M. Nishiura, X. Li, Z. Xi, and Z. Hou
  • Journal Title: Chem. Asian J. 3 Pages: 1406-1414
  • Peer Reviewed
• [Journal Article] Isoprene Polymerization with Yttrium Amidinate Catalyst : Switching the Regio- and Stereoselectivity by Addition of AlMe_3 (2008)
  • Author(s): L. Zhang, M. Nishiura, M. Yuki, Y. Luo, and Z. Hou
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 2642-2645
  • Peer Reviewed
• [Journal Article] Rare-Earth-Metal Mixed Hydride/Aryoxyide Complexes Bearing Mono(cyclopentadienyl) Ligands. Synthesis, CO_2 fixation, and Catalysis on Copolymerization of CO_2 with Cyclohexene Oxide (2008)
  • Author(s): D. Cui, M. Nishiura, O. Tradif, and Z. Hou
  • Journal Title: Organometallics 27 Pages: 2428-2435
  • Peer Reviewed
• [Journal Article] Synthesis and styrene polymerisation catalysis of ・^5- and ・^1-pyrrolyl-ligated cationic rare earth metal aminobenzyl complexes (2008)
  • Author(s): M. Nishiura, T, Mashiko, and Z. Hou
  • Journal Title: Chem. Commun. Pages: 2019-2021
  • Peer Reviewed
• [Journal Article] Half-Sandwich o-N,N-Dimethyl- aminobenzyl Complexes over the Full Size Range of Group 3 and Lanthanide Metals. Synthesis, Structural Characterization, and Catalysis of Phosphine P.H Bond Addition to Carbodiimides (2008)
  • Author(s): W.-X. Zhang, M. Nishiura, T. Mashiko, and Z. Hou
  • Journal Title: Chem. Eur. J. 14 Pages: 2167-2179
  • Peer Reviewed
• [Journal Article] Synthesis and Styrene Polymerisation Catalysis of η5- and η1-fiyrrolyl-Ligated Cationic Rare Earth Metal Aminobenzyl Complexes (2008)
  • Author(s): M. Nishiura
  • Journal Title: Chem. Commun. Pages: 2019-2021
  • Peer Reviewed
• [Journal Article] Synthesis of (Z)-1-Aza-1,3-enynes by the Cross-Coupling of Terminal Alkynes with Isocyanides Catalyzed by Rare-Earth Metal Complexes (2008)
  • Author(s): W. Zhang
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 9700-9703
  • Peer Reviewed
• [Journal Article] Cationic Scandium Allyl Complexes Bearing Mono(cyclopentadienyl) Ligands: Synthesis, Novel Structural Variety, and Olefin-Polymerization Catalysis (2008)
  • Author(s): N. Yu
  • Journal Title: Chem. Asian J. 3 Pages: 1406-1414
  • Peer Reviewed
• [Journal Article] Isoprene Polymerization with Yttrium Amidinate Catalysts: Switching the Regio- and Stereoselectivity by Addition of AlMe3 (2008)
  • Author(s): L. Zhang
  • Journal Title: Angew. Chem. Int. Ed 47 Pages: 2642-2645
  • Peer Reviewed
• [Journal Article] Rare-Earth-Metal Mixed Hydride/Aryloxide Complexes Bearing Mono(cyclopentadienyl) Ligands. Synthesis, CO2 Fixation, and Catalysis on Copolymerization of CO2 with Cyclohexene Oxide (2008)
  • Author(s): D. Cui
  • Journal Title: Organometallics 27 Pages: 2428-2435
  • Peer Reviewed
• [Journal Article] 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 (2007)
  • Author(s): L. Zhang, T. Suzuki, Y. Luo, M. Nishiura, and Z. Hou
  • Journal Title: Angew. Chem. Int. Ed. 46 Pages: 1909-1913
  • Peer Reviewed
• [Journal Article] Catalytic Addition of Amine N-H Bonds to Carbodiimides by Half-Sandwich Rare Earth Metal Complexes : Efficient Synthesis of Substituted Guanidines through Amine Protonolysis of Rare Earth Metal Guanidinates (2007)
  • Author(s): W. Zhang, M. Nishiura, and Z. Hou
  • Journal Title: Chem. Eur. J. 13 Pages: 4037-4051
  • Peer Reviewed
• [Journal Article] Synthesis and Reactions of Polynuclear Polyhydrido Rare Earth Metal Complexes Composed of "(C_5Me_4SiMe_3)LnH_2" Units : A New Frontier of Rare Earth Metal Hydride Chemistry(Selected as the Back Cover Picture, 10^<th> Anniversary Special Issue) (2007)
  • Author(s): Z. Hou, M. Nishiura, and T. Shima
  • Journal Title: Eur. J. Inorg. Chem. Pages: 2535-2545
  • Peer Reviewed
• [Journal Article] Cationic Scandium Aminobenzyl Complexes. Synthesis, Structure and Unprecedented Catalysis of Copolymerization of 1-Hexene and Dicyclopentadiene (2007)
  • Author(s): X. Li
  • Journal Title: Chem. Commun. Pages: 4137-4139
  • Peer Reviewed
• [Journal Article] Half-Sandwich o-N, N-Dimethylaminobenzyl Complexes over the Full Size Range of Group 3 and Lanthanide Metals. Synthesis, Structural Characterization, and Catalysis of Phosphine P-H bond Addition to Carbodiimides
  • Author(s): W. Zhang
  • Journal Title: Chem. Eur. J. (in press)
  • Peer Reviewed
• [Journal Article] Synthesis and Styrene Polymerisation Catalysis of η^5-and η^1-Pyrrolyl-Ligated Cationic Rare Earth Metal Aminobenzyl Complexes
  • Author(s): M. Nishiura
  • Journal Title: Chem. Commun. (in press)
  • Peer Reviewed
• [Presentation] 多核希土類ポリヒドリド錯体の新展開 (2008)
  • Author(s): 西浦正芳
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢
  • Year and Date: 2008-09-20
• [Presentation] ピロリル配位子を有する希土類ジアルキル錯体の合成と反応 (2008)
  • Author(s): 西浦正芳
  • Organizer: 第25回希土類討論会
  • Place of Presentation: 東京
  • Year and Date: 2008-05-29
• [Presentation] 多核希土類ポリヒドリド錯体の新展開 (2008)
  • Author(s): 西浦正芳、島隆則、今野陽介、侯 召民
  • Organizer: 第58回錯体化学討論会「希土類錯体 : 未踏配位化学の探究と機能創成」, S6-2
  • Place of Presentation: 金沢
• [Presentation] 全希土類元素における多核ポリヒドリド錯体の合成と反応性 (2008)
  • Author(s): 西浦正芳
  • Organizer: 第4回若手コロキウム
  • Place of Presentation: 函館
• [Presentation] ピロリル配位子を有する希土類ジアルキル錯体の合成と反応 (2008)
  • Author(s): 西浦正芳、増子智洋、侯 召民
  • Organizer: 第25回希土類討論会, 1C-08
  • Place of Presentation: 東京
• [Presentation] 軽希土類ポリヒドリド錯体の合成と反応性 (2007)
  • Author(s): 西浦正芳
  • Organizer: 第57回錯体化学討論会
  • Place of Presentation: 名古屋工業大学
  • Year and Date: 2007-09-25
• [Presentation] 全希土類元素におけるハーフサンドイッチビスアルキル錯体の合成と新規ポリヒドリド錯体への展開 (2007)
  • Author(s): 西浦正芳
  • Organizer: 第24回希土類討論会
  • Place of Presentation: 九州大学医学部百年講堂
  • Year and Date: 2007-05-18
• [Presentation] 軽希土類ポリヒドリド錯体の合成と反応性 (2007)
  • Author(s): 西浦正芳, 今野陽介, 侯 召民
  • Organizer: 第57回錯体化学討論会, 1D-05
  • Place of Presentation: 名古屋
• [Presentation] 全希土類元素におけるハーフサンドイッチビスアルキル錯体の合成と新規ポリヒドリド錯体への展開 (2007)
  • Author(s): 西浦正芳、侯 召民
  • Organizer: 第24回希土類討論会, 2C-11
  • Place of Presentation: 福岡
• [Book] "希土類触媒による高分子重合", 希土類の材料技術ハンドブック (2008)
  • Author(s): 西浦正芳、侯召民
  • Publisher: エヌ・ティー・エス
• [Book] 希土類の材料技術ハンドブック (2008)
  • Author(s): 西浦正芳
  • Total Pages: 9
  • Publisher: エヌ・ティー・エス
• [Book] 希土類の材料技術
  • Author(s): 西浦正芳
  • Publisher: エヌ・ティー・エス(in press)
• [Remarks]
  • URL: http://www.riken.jp/lab-www/organometallic/index.html
• [Remarks]
  • URL: http://www.riken.jp/lab-www/organometallic/index.html
• [Remarks]
  • URL: http://www.riken.jp/lab-www/organometallic/index.html
• [Patent(Industrial Property Rights)] 重合体およびそれを用いた光学材料 (2009)
  • Inventor(s): 西浦正芳、侯召民、藤堂昭、木津巧一
  • Industrial Property Rights Holder: (独)理化学研究所、三井化学(株)
  • Industrial Property Number: 2009-083795
  • Filing Date: 2009-03-30
• [Patent(Industrial Property Rights)] 複素環配位子を含む金属錯体, 及びそれを含む重合触媒組成物 (2007)
  • Inventor(s): 西浦正芳, 増子智洋, 侯召民
  • Industrial Property Rights Holder: (独)理化学研究所
  • Industrial Property Number: 2007-060121
  • Filing Date: 2007-03-09