Development of High- and Low-valent Early Transition Metal Catalysts for Carbon-Carbon Bond Forming Reaction

• Project/Area Number: 21750101
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Osaka University
• Principal Investigator: TSURUGI Hayato Osaka University, 大学院・基礎工学研究科, 講師 (60432514)
• Project Period (FY): 2009 – 2010
• Project Status: Completed (Fiscal Year 2010)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2010: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2009: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
• Keywords: 炭素-水素結合活性化 / 前周期遷移金属錯体 / 低原子価錯体 / 酸化還元 / カップリング反応

Research Abstract

We developed a novel oxidant-free cross dehydrogenative coupling reaction of 2,6-lutidine and internal alkynes leading to five-membered carbocyclic compounds by non-metallocene cationic hafnium alkyl complexes. We also found that mild and salt-free reduction of MCl_5 (M=Nb, Ta) was achieved by using 3,6-bis(trimethylsilyl)-1,4-hexadiene derivatives as reducing reagents. The salt contact free low-valent TaCl_3 exhibits high catalytic activity for the trimerization of ethylene to 1-hexene (>1000 TOF) with excellent selectivity (>98%).

Research Products

• [Journal Article] Oxidant-Free Direct Coupling of Internal Alkynes and 2-Alkylpyridine via Double C.H Activations by Alkylhafnium Complexes (2011)
  • Author(s): 劒隼人、山本浩二、真島和志
  • Journal Title: Journal of American Chemical Society 32巻 Pages: 732-735
  • Peer Reviewed
• [Journal Article] Oxidant-Free Direct Coupling of Internal Alkynes and 2-Alkylpyridinevia Double C-H Activations by Alkylhafnium Complexes (2011)
  • Author(s): 劒隼人、真島和志, 他1名
  • Journal Title: Journal of American Chemical Society Volume: Vol.132 Pages: 732-735
  • Peer Reviewed
• [Journal Article] Carboxylate Ligand-Induced Intramolecular C.H Bond Activation of Iridium Complexes with N-Phenylperimidine-Based Carbene Ligands (2010)
  • Author(s): 劒隼人、真島和志, 他5名
  • Journal Title: Organometallics 29巻 Pages: 4120-4129
  • Peer Reviewed
• [Journal Article] Intramolecular Alkylation of α-Diimine Ligands Giving Amido.imino and Diamido Scandium and Yttrium Complexes as Catalysts for Intramolecular Hydroamination/ Cyclization (2010)
  • Author(s): 劒隼人、真島和志, 他2名
  • Journal Title: Organometallics 29巻 Pages: 3463-3466
  • Peer Reviewed
• [Journal Article] Salt Metathesis and Direct Reduction Reactions Leading to Group 3 Metal Complexes with a N,N'-Bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene Ligand and Their Solid-State Structures (2010)
  • Author(s): 劒隼人、真島和志, 他3名
  • Journal Title: Organometallics 29巻 Pages: 2610-2615
  • Peer Reviewed
• [Journal Article] Highly Reactive Metal-Nitrogen Bond Induced C-H Bond Activation and Azametallacycle Formation (2010)
  • Author(s): 劒隼人、真島和志, 他4名
  • Journal Title: Organometallics 29巻 Pages: 34-37
  • Peer Reviewed
• [Journal Article] Salt Metathesis and Direct Reduction Reactions Leading to Group 3 Metal Complexes with a N,N'-Bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene Ligand and Their Solid-State Structures (2010)
  • Author(s): 劒隼人、真島和志, 他3名
  • Journal Title: Organometallics Volume: Vol.29 Pages: 2610-2615
  • Peer Reviewed
• [Journal Article] Intramolecular Alkylation of α-Diimine Ligands Giving Amido-imino and Diamido Scandium and Yttrium Complexes as Catalysts for Intramolecular Hydroamination/Cyclization (2010)
  • Author(s): 劒隼人、真島和志, 他2名
  • Journal Title: Organometallics Volume: Vol.29 Pages: 3463-3466
  • Peer Reviewed
• [Journal Article] Carboxylate Ligand-Induced Intramolecular C-H Bond Activation of Iridium Complexes with N-Phenylperimidine-Based Carbene Ligands (2010)
  • Author(s): 劒隼人、真島和志, 他5名
  • Journal Title: Organometallics Volume: Vol.29 Pages: 4120-4129
  • Peer Reviewed
• [Journal Article] Highly Reactive Metal-Nitrogen Bond Induced C-H Bond Activation and Azametallacycle Formation (2010)
  • Author(s): Panda Tarun、劒隼人、真島和志, 他3名
  • Journal Title: Organometallics Volume: Vol.29 Pages: 34-37
  • Peer Reviewed
• [Journal Article] New Tantalum Ligand-Free Catalyst System for Highly Selective Trimerization of Ethylene Affording 1-Hexene : New Evidence of a Metallacycle Mechanism、 (2009)
  • Author(s): 劒隼人、真島和志, 他4名
  • Journal Title: Journal of American Chemical Society 131巻 Pages: 5370-5371
  • Peer Reviewed
• [Journal Article] Tantalum-Benzylidene Complexes Supported by C5Me5 and Diazadiene Ligands: Synthesis, Kinetic Analysis of the Formation, and Reactive Studies (2009)
  • Author(s): 劒隼人、真島和志, 他3名
  • Journal Title: Organometallics 28巻 Pages: 1950-1960
  • Peer Reviewed
• [Journal Article] Tantalum-Benzylidene Complexes Supported by C_5Me_5 and Diazadiene Ligands : Synthesis, Kinetic Analysis of the Formation, and Reactive Studies (2009)
  • Author(s): 劒隼人、真島和志, 他3名
  • Journal Title: Organometallics Volume: Vol.28 Pages: 1950-1960
  • Peer Reviewed
• [Journal Article] New Tantalum Ligand-Free Catalyst System for Highly Selective Trimerization of Ethylene Affording 1-Hexene : New Evidence of a Metallacycle Mechanism (2009)
  • Author(s): Arteaga-Muller Rocio、劒隼人、真島和志, 他3名
  • Journal Title: Journal of American Chemical Society Volume: Vol.131 Pages: 5370-5371
  • Peer Reviewed
• [Presentation] Redox behavior of group 5 metal complexes with 1,4-diaza-1,3-butadiene ligands and their activity for carbon-halogen bond activation (2011)
  • Author(s): 劒隼人、真島和志, 他2名
  • Place of Presentation: アナハイムコンベンションセンター(アメリカ合衆国)
  • Year and Date: 2011-03-29
• [Presentation] Coupling reaction of 2-alkylpyridine with alkynes catalyzed by alkylhafnium complexes (2011)
  • Author(s): 劒隼人、山本浩二、真島和志
  • Place of Presentation: アナハイムコンベンションセンター(アメリカ合衆国)
  • Year and Date: 2011-03-29
• [Presentation] Redox behavior of group 5 metal complexes with 1,4-diaza-1,3-butadiene ligands and their activity for carbon-halogen bond activation (2011)
  • Author(s): 劒隼人、真島和志, 他2名
  • Organizer: ACS Spring Conference
  • Place of Presentation: アメリカ合衆国:カリフォルニア、アナハイム
  • Year and Date: 2011-03-29
• [Presentation] Coupling reaction of 2-alkylpyridine with alkynes catalyzed by alkylhafnium complexes (2011)
  • Author(s): 劒隼人、真島和志, 他1名
  • Organizer: ACS Spring Conference
  • Place of Presentation: アメリカ合衆国:カリフォルニア、アナハイム
  • Year and Date: 2011-03-29
• [Presentation] Controlled benzylation of α-diimine ligands leading to mono- and bis(amido)M(CH_2Ph)_n (n=2,3) complexes as catalyst precursors for polymerization of α-olefins (2010)
  • Author(s): 劒隼人、真島和志, 他2名
  • Place of Presentation: ヒルトンハワイアンビレッジ(アメリカ合衆国)
  • Year and Date: 2010-12-17
• [Presentation] Controlled benzylation of α-diimine ligands leading to mono- and bis(amido)M(CH_2Ph)_n(n=2,3) complexes as catalyst precursors for polymerization of α-olefins (2010)
  • Author(s): 劒隼人、真島和志, 他3名
  • Organizer: The International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: アメリカ合衆国:ハワイ、ホノルル
  • Year and Date: 2010-12-17
• [Presentation] Preparation of Group 3 Metal Complexes with N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene Ligand via Salt Metathesis and Direct Reduction Reactions (2010)
  • Author(s): 劒隼人、真島和志, 他2名
  • Place of Presentation: ヒルトンハワイアンビレッジ(アメリカ合衆国)
  • Year and Date: 2010-12-15
• [Presentation] Preparation of Group 3 Metal Complexes with N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene Ligand via Salt Metathesis and Direct Reduction Reactions (2010)
  • Author(s): 劒隼人、真島和志, 他3名
  • Organizer: The International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: アメリカ合衆国:ハワイ、ホノルル
  • Year and Date: 2010-12-15
• [Presentation] Hafnium-carbon Bond Mediated C-H Bond Activation of Heteroaromatic Compounds (2010)
  • Author(s): 劒隼人、山本浩二、真島和志
  • Organizer: International Symposium on Environmentally Benign Synthesis
  • Place of Presentation: 中之島センター(大阪)
  • Year and Date: 2010-10-22
• [Presentation] Hafnium-carbon Bond Mediated C-H Bond Activation of Heteroaromatic Compounds (2010)
  • Author(s): 劒隼人、真島和志, 他1名
  • Organizer: International Symposium on Environmentally Benign Synthesis
  • Place of Presentation: 大阪市:中之島センター
  • Year and Date: 2010-10-22
• [Presentation] Dimolybdenum Complexes Catalyzed Atom Transfer Radical Addition and Polymerization : Detection of Dormant Dimolybdenum Species (2010)
  • Author(s): 劒隼人、真島和志, 他4名
  • Organizer: 60^<th> Anniversary Conference on Coordination Chemistry in OSAKA
  • Place of Presentation: 大阪国際交流センター
  • Year and Date: 2010-09-27
• [Presentation] Dimolybdenum Complexes Catalyzed Atom Transfer Radical Addition and Polymerization : Detection of Dormant Dimolybdenum Species (2010)
  • Author(s): 劒隼人、真島和志, 他4名
  • Organizer: 60^<th> Anniversary Conference on Coordination Chemistry in OSAKA
  • Place of Presentation: 大阪市:大阪国際交流センター
  • Year and Date: 2010-09-27
• [Presentation] Group 4 Metal.Nitrogen Bond Mediated C-H Bond Activation Leading to Azametallacycle Complexes、 (2010)
  • Author(s): 劒隼人、真島和志, 他3名
  • Organizer: 24^<th> International Conference on Organometallic Chemistry
  • Place of Presentation: 台北国際会議場(台湾)
  • Year and Date: 2010-07-18
• [Presentation] Group 4 Metal-Nitrogen Bond, Mediated C-H Bond Activation Leading to Azametallacycle Complexes (2010)
  • Author(s): 劒隼人、真島和志, 他3名
  • Organizer: 24^<th> International Conference on Organometallic Chemistry
  • Place of Presentation: 台湾:台北
  • Year and Date: 2010-07-18
• [Presentation] Intramolecular Alkylation of α-Diimine Ligands Bound to Scandium and Yttrium Leading to Mono- and bis(amido)Ln(CH_2SiMe_3)n Complexes (Ln=Sc, Y ; n=1,2) as Catalysts for Intramolecular Hydroamination/ cyclization (2010)
  • Author(s): 劒隼人、真島和志, 他2名
  • Organizer: International Symposium on Organometallic Chemistry 2010
  • Place of Presentation: The Chinese University of Hong Kong(中国)
  • Year and Date: 2010-07-16
• [Presentation] Intramolecular Alkylation of α-Diimine Ligands Bound to Scandium and Yttrium Leading to Mono- and bis(amido)Ln(CH_2SiMe_3)_n Complexes (Ln=Sc, Y;n=1,2) as Catalysts for Intramolecular Hydroamination/cyclization (2010)
  • Author(s): 劒隼人、真島和志, 他2名
  • Organizer: International Symposium on Organometallic Chemistry 2010
  • Place of Presentation: 中国:香港
  • Year and Date: 2010-07-16
• [Presentation] 6族金属2核錯体を触媒としたスチレンおよびメタクリル酸エステルのラジカル重合反応 (2010)
  • Author(s): 劒隼人、真島和志, 他3名
  • Organizer: 第59回高分子学会年次大会
  • Place of Presentation: パシフィコ横浜
  • Year and Date: 2010-05-27
• [Presentation] 6族金属2核錯体を触媒としたスチレンおよびメタクリル酸エステルのラジカル重合反応 (2010)
  • Author(s): 劒隼人、真島和志, 他3名
  • Organizer: 第59回高分子学会年次大会
  • Place of Presentation: 横浜市:パシフィコ横浜
  • Year and Date: 2010-05-27
• [Presentation] グアニジネート一置換型白金四核クラスターの合成とその超分子合成への応用 (2010)
  • Author(s): 劒隼人、真島和志, 他1名
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪市:近畿大学
  • Year and Date: 2010-03-29
• [Presentation] pyphosを配位子としたMoおよびCuクラスターの溶媒交換反応 (2010)
  • Author(s): 劒隼人、真島和志, 他2名
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪市:近畿大学
  • Year and Date: 2010-03-28
• [Presentation] 1,4-ジアザ-1,3-ブタジエン配位子を有するランタノイド錯体の合成と構造 (2010)
  • Author(s): 劒隼人、真島和志, 他2名
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪市:近畿大学
  • Year and Date: 2010-03-27
• [Presentation] ハフニウム錯体を用いた複素環化合物と不飽和炭化水素の触媒的カップリング反応 (2010)
  • Author(s): 劒隼人、真島和志, 他1名
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪市:近畿大学
  • Year and Date: 2010-03-27
• [Presentation] ビス(シリル)シクロヘキサジエン誘導体によるMCl5(M=Nb,Ta)の還元反応を利用した酸化還元活性な配位子を有するニオブ・タンタル錯体の合成 (2010)
  • Author(s): 劒隼人、真島和志, 他1名
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪市:近畿大学
  • Year and Date: 2010-03-27
• [Presentation] モリブデン2核錯体を触媒とするラジカル反応の最適化と活性種の捕捉 (2010)
  • Author(s): 劒隼人、真島和志, 他1名
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪市:近畿大学
  • Year and Date: 2010-03-27
• [Presentation] (η4-1,4-ジアミノ-1,4-ジアザ-1,3-ブタジエン)イリジウム誘導体の合成とアルデヒドの縮合反応による多核化 (2010)
  • Author(s): 劒隼人、真島和志, 他1名
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪市:近畿大学
  • Year and Date: 2010-03-27
• [Presentation] カルベン配位子を有するイリジウム(I)およびイリジウム(III)錯体の合成とその反応性 (2010)
  • Author(s): 劒隼人、真島和志, 他1名
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪市:近畿大学
  • Year and Date: 2010-03-27
• [Presentation] 4族金属-窒素結合による炭素-水素結合活性化を利用したアザメタラサイクルの形成 (2010)
  • Author(s): 劒隼人、真島和志, 他3名
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪市:近畿大学
  • Year and Date: 2010-03-27
• [Presentation] Synthesis of Amido-imino and Diamido Complexes of Group 3 Metals and Catalystic Performances for Hydroamination of Unactivated Terminal Alkene (2009)
  • Author(s): 劒隼人、真島和志, 他2名
  • Organizer: International Sysmposium on Bio-Environmental Chemistry
  • Place of Presentation: 吹田市、ホテル阪急エキスポパーク
  • Year and Date: 2009-12-20
• [Presentation] Mild and Salt-free Reduction of MCl5(M=Nb, Ta) by Bis(silyl)cyclohexadienes and Their Application to Selective Trimerization of Ethylene to 1-Hexene (2009)
  • Author(s): 劒隼人、真島和志, 他4名
  • Organizer: The 11th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-11)
  • Place of Presentation: 京都市、リーガロイヤルホテル京都
  • Year and Date: 2009-11-11
• [Presentation] Alkylative Construction of Amido-imino and Diamido Complexes of Group 3 Metals as Catalysts for Hydroamination of Unactivated Terminal Alkene (2009)
  • Author(s): 劒隼人、真島和志, 他2名
  • Organizer: 5th Spanish-Portuguese-Japanese Organic Chemistry Symposium
  • Place of Presentation: 吹田市、大阪大学
  • Year and Date: 2009-11-07
• [Presentation] モリブデン2核錯体を触媒としたラジカル反応の開発 (2009)
  • Author(s): 劒隼人、真島和志, 他1名
  • Organizer: 第104回触媒討論会
  • Place of Presentation: 宮崎市、宮崎大学・シーガイヤ宮崎
  • Year and Date: 2009-09-30
• [Presentation] 白金四核クラスターの置換活性部位の精密制御を鍵とする新規クラスターの合成 (2009)
  • Author(s): 劒隼人、真島和志, 他1名
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎市:長崎大学
  • Year and Date: 2009-09-26
• [Presentation] グアニジンおよびアミドーイミノ配位子を有する4族金属アミド錯体のワンポット合成と金属-窒素結合による炭素-水素結合の活性化 (2009)
  • Author(s): 劒隼人、真島和志, 他3名
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎市:長崎大学
  • Year and Date: 2009-09-25
• [Presentation] α-ジイミン配位子の選択的アルキル化による新規3族金属アミドーイミノおよびジアミド錯体の合成とヒドロアミノ化反応への展開 (2009)
  • Author(s): 劒隼人、真島和志, 他2名
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎市:長崎大学
  • Year and Date: 2009-09-25
• [Presentation] モリブデン2核錯体の酸化還元電位の広範囲な電位幅を利用したラジカル反応の制御 (2009)
  • Author(s): 劒隼人、真島和志, 他1名
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎市:長崎大学
  • Year and Date: 2009-09-25
• [Presentation] ビス(シリル)シクロヘキサジエンを還元剤とする3価タンタル種の新しい発生法とエチレンの触媒的3量化反応 (2009)
  • Author(s): 劒隼人、真島和志, 他4名
  • Organizer: 第56回有機金属化学討論会
  • Place of Presentation: 京都市、同志社大学今出川キャンパス
  • Year and Date: 2009-09-10
• [Presentation] Synthesis of Group 4 Metal Alkyl Complexes Bearing Dianionic N,N,C-Tridentate Ligands and Their Reactivity toward Heteroaromatic Substrates (2009)
  • Author(s): 劒隼人、真島和志, 他1名
  • Organizer: The 3^<rd> International Symposium on Synergy of Elements
  • Place of Presentation: 札幌市:北海道大学
  • Year and Date: 2009-08-29
• [Presentation] TaCl_5/Bis(silyl)cyclohexadiene Catalyzed Selective Trimerization of Ethylene to I-Hexene (2009)
  • Author(s): 劒隼人、真島和志, 他4名
  • Organizer: The 3^<rd> International Symposium on Synergy of Elements
  • Place of Presentation: 札幌市:北海道大学
  • Year and Date: 2009-08-29
• [Presentation] 1,4-Diaza-1,3-butadiene Complexes of Lanthanides : Syntheses, Structures, and Reactivity (2009)
  • Author(s): 劒隼人、真島和志, 他2名
  • Organizer: 第26回希土類討論会
  • Place of Presentation: 札幌市:札幌コンベンションセンター
  • Year and Date: 2009-05-29