Precision Designing of Multinuclear Transition Metal Complexes

• Project/Area Number: 18064007
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: SUZUKI Hiroharu Tokyo Institute of Technology, 大学院・理工学研究科, 教授 (30106629)
• Co-Investigator(Kenkyū-buntansha): TAKAO Toshiro 東京工業大学, 大学院・理工学研究科, 准教授 (00313346)
• Project Period (FY): 2006 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥76,100,000 (Direct Cost: ¥76,100,000); Fiscal Year 2009: ¥9,800,000 (Direct Cost: ¥9,800,000); Fiscal Year 2008: ¥9,800,000 (Direct Cost: ¥9,800,000); Fiscal Year 2007: ¥9,800,000 (Direct Cost: ¥9,800,000); Fiscal Year 2006: ¥46,700,000 (Direct Cost: ¥46,700,000)
• Keywords: 異種金属クラスター / 異種金属効果 / ポリヒドリド錯体 / ルテニウム / 相乗作用 / ポリヒドリドクラスター / ルテニウムクラスター / オスミウムクラスター / アンモニア活性化 / イリジウムクラスター / ロジウムクラスター / オスミウム / 速度論的異種金属効果 / 熱力学的異種金属効果 / クラスター錯体 / ポリヒドリド / 水素分子活性化 / ホモリシス / 架橋イミド錯体 / 三核クラスター

Research Abstract

Significant heterometallic effects, such as marked regioselectivity and remarkable acceleration, were observed in the reactions of di- and trinuclear Ru-Os polyhydrido clusters with tertiary phosphoruscompounds or ammonia.

Research Products

• [Journal Article] Synthesis and Structure of a Novel Ruthenium Hydrido Bis(dihydrogen) Complex with 1, 4, 7-Trimethyl-1, 4, 7-triazacyclononae Ligand: A Useful Precursor for Synthesis of Heterometallic Complexes (2010)
  • Author(s): Shima, T.; Namura, K.; Kameo, H.; Suzuki, H.
  • Journal Title: Organometallics 29 Pages: 337-346
  • Peer Reviewed
• [Journal Article] Synthesis and Structure of a Novel Ruthenium Hydrido Bis(dihydrogen)Complex with 1,4,7-Trimethl-1,4,7-triazacyclononae Ligand : A Useful Precursor for Synthesis of Heterometallic Complexes (2010)
  • Author(s): 島隆則、名村響、亀尾肇、鈴木寛治
  • Journal Title: Organometallics 29 Pages: 337-346
  • Peer Reviewed
• [Journal Article] Arylation of a Hydrocarbyl Ligand Formed from n-Alkane via C-H Bond Activation of Benzene using a Triruthenium Cluster (2009)
  • Author(s): Moriya, M.; Tahara, A.; Takao, T.; Suzuki, H. Eur. J.
  • Journal Title: Inorg. Chem. Pages: 3393-3397
  • Peer Reviewed
• [Journal Article] Synthesis of Heterometallic Trinuclear Polyhydrido Clusters Containing Ruthenium and Osmium and Their Electronic and Structural Deviation from Homometallic Systems (2009)
  • Author(s): Kameo, H.; Shima, T.; Nakajima, Y.; Suzuki, H.
  • Journal Title: Organometallics 28 Pages: 2535-2545
  • Peer Reviewed
• [Journal Article] Heterometallic Trinuclear Polyhydrido Complexes Containing Ruthenium and a Group 9 Metal, [Cp3Ru2M(μ3-H)(μ-H)3] (M = Ir or Rh; Cp =η5-C5Me5): Synthesis, Structure, and Site Selectivity in Reactions with Phosphines (2009)
  • Author(s): Shima, T.; Sugimura, Y.; Suzuki, H.
  • Journal Title: Organometallics 28 Pages: 871-881
  • Peer Reviewed
• [Journal Article] Synthesis of Heterometallic Trinuclear Polyhydrido Clusters Containing Ruthenium and Osmium and Their Electronic and Structural Deviation from Homometallic Systems (2009)
  • Author(s): 亀尾肇、島隆則、中島裕美子、鈴木寛治
  • Journal Title: Organometallics 28 Pages: 2535-2545
  • Peer Reviewed
• [Journal Article] Zirconocene-Iridium Hydrido Complexes : Arene Carbon-Hydrogen Bond Activation and Formation of a Planar Square Zr_2Ir_2 Complex (2009)
  • Author(s): 大石理貴、鈴木寛治
  • Journal Title: Inorg.Chem 48 Pages: 2349-2351
  • Peer Reviewed
• [Journal Article] Heterometallic Trinuclear Poluhydrido Complexes Containing Ruthenium and a Group 9 Metals, [Cp'3Ru2M(μ3-H)(μ-H)3] (M = Ir or Rh;Cp'=η5-C5Me5): Synthesis, Structure, and Site Selectivity in Reactions with Phosphines (2009)
  • Author(s): 島 隆則、杉村ゆみ、鈴木寛治
  • Journal Title: Organometallics 28 Pages: 871-881
  • Peer Reviewed
• [Journal Article] Drastic acceleration of phosphine/phosphite incorporation into a tetrahydrido ruthenium/osmium complex, and one-way ruthenium to osmium migration of a phosphorus ligand (2008)
  • Author(s): Kameo, H.; Nakajima, Y.; Suzuki, H.
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 10159-10162
  • Peer Reviewed
• [Journal Article] Synthesis of Trinuclear Osmium Polyhydrido Clusters [{(C5Me5)Os}3(μ-H)6]+ and {(C5Me5)Os}3(μ-H)3(μ3-H)2 and Comparison with the Ruthenium Analogues (2008)
  • Author(s): Kameo, H.; Suzuki, H.
  • Journal Title: Organometallics 27
  • Peer Reviewed
• [Journal Article] Insertion of Acetylene and Nitriles into a Ru-C Bond of a Dicationic Triruthenium Complex Having aμ3-η3-C3 Ring: Formation of Six-Membered Ruthenacycles on a Triruthenium Core (2008)
  • Author(s): Takao, T.; Moriya, M.; Suzuki, H.
  • Journal Title: Organometallics 27 Pages: 1044-1054
  • Peer Reviewed
• [Journal Article] Introduction of a Methoxy Group into a Hydrocarbyl Ligand Derived from a Linear Alkane on a Triruthenium Cluster via Chemical Oxidation (2008)
  • Author(s): Takao, T.; Moriya, M.; Suzuki, H.
  • Journal Title: Organometallics 27 Pages: 18-20
  • Peer Reviewed
• [Journal Article] Synthesis of Trinuclear Osmium Polyhydrido Clusters [{(C5Me5)Os}3(μ-H)6]+ and {(C5Me5)Os}3(μ-H)3(μ3-H)2 and Comparison with the Ruthenium Analogues (2008)
  • Author(s): 亀尾 肇、鈴木寛治
  • Journal Title: Organometallics 27 Pages: 4248-4253
  • Peer Reviewed
• [Journal Article] Drastic acceleration of phosphine/phosphate incorporation into a tetrahydride ruthenium/osmium complex, and one-way ruthenium to osmium migration of a phosphorus ligand (2008)
  • Author(s): 亀尾 肇、中島裕美子、鈴木寛治
  • Journal Title: Angew. Chem. Int Ed. 47 Pages: 10159-10162
  • Peer Reviewed
• [Journal Article] Drastic Acceleration of Phosphine/Phosphite Incorporation into a... (2008)
  • Author(s): 亀尾肇、中島裕美子、鈴木寛治
  • Journal Title: Angew. Chem. Int. Ed 47 Pages: 10159-10162
  • Peer Reviewed
• [Journal Article] Reaction of Heterobimetallic Polyhydrido Cluster, [Cp^*Ru(μ^-H)_4OsCp^*] (2008)
  • Author(s): 島隆則、市川利明、鈴木寛治
  • Journal Title: Organometallics 26 Pages: 6329-6337
  • Peer Reviewed
• [Journal Article] Heterometallic Trinuclear Polyhydrido Complexes Containing (2008)
  • Author(s): 島隆則、杉村ゆみ、鈴木寛治
  • Journal Title: Organometallics 28 Pages: 871-881
  • Peer Reviewed
• [Journal Article] Reaction of a Heterobimetallic Polyhydrido Cluster, [Cp*Ru(μ-H)4OsCp*] (Cp* =η5-C5Me5), with Diphenylacetylene. Regioselective C-H Bond Activation at the Osmium Center (2007)
  • Author(s): Shima, T.; Ichikawa, T.; Suzuki, H.
  • Journal Title: Organometallics 26 Pages: 6329-6337
  • Peer Reviewed
• [Journal Article] Hydrogenation of a Trinuclearμ3-Imido Complex of Ruthenium: Homolytic or Heterolytic H-H Bond Cleavage? (2007)
  • Author(s): Kameo, H.; Nakajima, Y.; Suzuki, H. Eur. J.
  • Journal Title: Inorg. Chem. Pages: 1793-1798
  • Peer Reviewed
• [Journal Article] Ruthenium Polyhydrido Clusters Having a Bridging Alkylzinc Group, [(η5-C5Me5) Ru(μ-H)]3(μ3-ZnR)n(μ3-H)2-n and [(η5-C5Me5) Ru]2(μ-ZnR)n(μ-H)4-n (R = Me and Et; n = 1 and 2) (2007)
  • Author(s): Ohashi, M.; Matsubara, K.; Suzuki, H.
  • Journal Title: Organometallics 26 Pages: 2330-2339
  • Peer Reviewed
• [Journal Article] Synthesis and Structure of Cationic Triruthenium Complexes Containing an Oxametallacycle; Reversible Carbon-Oxygen Bond Formation and Scission on an Electron-Deficient Triruthenium Plane (2007)
  • Author(s): Moriya, M.; Takao, T,; Suzuki, H.
  • Journal Title: Organometallics 26 Pages: 1650-1657
  • Peer Reviewed
• [Journal Article] Redox-induced Reversible Rearrangement of a Dimetalloallyl Ligand on the Trinuclear Cluster of Ruthenium. Mechanistic Aspects of Formation of the Face-cappingμ3-C3 Ring on the Triruthenium Plane (2007)
  • Author(s): Takao, T.; Moriya, M.; Suzuki, H.
  • Journal Title: Organometallics 26 Pages: 1349-1360
  • Peer Reviewed
• [Journal Article] Ruthenium Polyhydrido Clusters Having a Bridging Alkylzinc Group, [(η^5-C_5Me_5)Ru(μ_3-ZnR)_n(μ_3-H)_<2-n> and [(η^5-C_5Me_5)Ru]_2(μ-ZnR)_n(μ-H)_<4-n> (R=Me and Et; n=1 and 2) (2007)
  • Author(s): Masato Ohashi, Kouki Matsubara, Hiroharu Suzuki,
  • Journal Title: Organometallics 26 Pages: 2330-2339
  • Peer Reviewed
• [Journal Article] Hydrogenation of a Trinuclear μ_3-Imido Complex of Ruthenium: Homolytic or Heterolytic H-H Bond Cleavage? (2007)
  • Author(s): Hajime Kameo, Yumiko Nakajima, Hiroharu Suzuki
  • Journal Title: Eur. J. Inorg. Chem. Pages: 1793-1798
  • Peer Reviewed
• [Journal Article] Reaction of a Heterobimetallic Polyhydrido Cluster, [Cp*Ru(μ-H)_4OsCp*] (Cp*=η^5-C_5Me_5), with Diphenylacetylene. Regioselective C-H Bond Activation at the Osmium Center (2007)
  • Author(s): Takanori Shima, Toshiaki Ichikawa, Hiroharu Suzuki
  • Journal Title: Organometallics 26 Pages: 6329-6337
  • Peer Reviewed
• [Journal Article] Redox-induced Reversible Rearrangement of a Dimetalloallyl Ligand on the Trinuclear Cluster of Ruthenium. Mechanistic Aspects of Formation of the Face-capping μ_3-C_3 Ring on the Triruthenium Plane (2007)
  • Author(s): Toshiro Takao, Makoto Moriya, Hiroharu Suzuki
  • Journal Title: Organometallics 26・6 Pages: 1349-1360
• [Journal Article] Synthesis and Structure of Cationic Triruthenium Complexes Containing an Oxametallacycle; Reversible Carbon-Oxygen Bond Formation and Scission on an Electron-Deficient Triruthenium Plane (2007)
  • Author(s): Makoto Moriya, Toshiro Takao, Hiroharu Suzuki
  • Journal Title: Organometallics 26・7 Pages: 1650-1657
• [Journal Article] Trinuclear Ru/Os Clusters : Compounds with Hydrocarbon Ligands (Cyclopentadienyls) (2007)
  • Author(s): Hiroharu Suzuki, Toshiro Takao
  • Journal Title: Comprehensive Organometallic Chemistry III 6 Pages: 797-821
• [Journal Article] Hydrogenation of a Trinuclear m3-Imido Complex of Ruthenium : Homolytic or Heterolytic H-H Bond Cleavage?
  • Author(s): Hajime Kameo, Yumiko Nakajima, Hiroharu Suzuki
  • Journal Title: Eur. J Inorg. Chem (in press)
• [Journal Article] Ruthenium Polyhdrido Clusters Having a Bridging Alkylzinc Group, [(η^5-C_5Me_5)Ru(μ-H)]_3(μ_3-ZnR)_n(μ_3-H)_<2-n> and [(η^5-C_5Me_5)Ru]_2(μ-ZnR)_n(μ-H)_<4-n> (R=Me and Et; n=1 and 2)
  • Author(s): Masato Ohashi, Kouki Matsubara, Hiroharu Suzuki
  • Journal Title: Organometallics (in press)
• [Presentation] 遷移金属クラスター反応場の構築とクラスター反応の開発 (2009)
  • Author(s): 鈴木寛治
  • Organizer: 第104回触媒討論会
  • Place of Presentation: 宮崎大学
  • Year and Date: 2009-09-30
• [Presentation] 遷移金属クラスタ-反応場の構築とクラスタ-反応の開発 (2009)
  • Author(s): 鈴木寛治
  • Organizer: 第104回触媒化学討論会
  • Place of Presentation: 宮崎大学
  • Year and Date: 2009-09-30
• [Presentation] Activation of Nitrogen-Hydrogen Bonds of Ammonia Induced by Trinuclear Polyhydrido Clusters Containing Ruthenium and Osmium (2009)
  • Author(s): Kameo, H.; Nakajima, Y.; Suzuki, H.
  • Organizer: 第55回有機金属化学討論会
  • Place of Presentation: 大阪府立大学
  • Year and Date: 2009-09-29
• [Presentation] トリアザシクロノナンを支持配位子とするルテニウムポリヒドリド錯体の合成と反応 (2009)
  • Author(s): 名村響, 亀尾肇, 鈴木寛治
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎大学
  • Year and Date: 2009-09-26
• [Presentation] Synthesis and Properties of Ruthenium Polyhydrido Complexes Having Two Ru2H4 Moieties Linked by Flexible Carbon Chains (2009)
  • Author(s): Yanagi, T.; Oishi, M.; Suzuki, H.
  • Organizer: 第56回有機金属化学討論会
  • Place of Presentation: 同志社大学
  • Year and Date: 2009-09-10
• [Presentation] 四核ルテニウムポリヒドリド錯体(CpRu)n(Cp*Ru)(4-n)H(6-m) (n=0, 1, 2, 3, 4; m = 1, 0, 1, 2)の電子的性質の評価 (2009)
  • Author(s): 亀尾肇, 望月信介, 伊藤大, 上原直樹, 藤本順子, 鈴木寛治
  • Organizer: 日本化学会第89回春季年会
  • Place of Presentation: 日本大学
  • Year and Date: 2009-03-29
• [Presentation] 架橋型ビステトラメチルシクロペンタジエニル配位子を有する四核ルテニウム架橋ベンゾキノン錯体の合成 (2009)
  • Author(s): 柳貴子, 大石理貴, 鈴木寛治
  • Organizer: 日本化学会第89回春季年会
  • Place of Presentation: 日本大学
  • Year and Date: 2009-03-29
• [Presentation] 四核ルテニウムポリヒドリド錯体(CpRu)n(Cp*Ru)4nH6m(n=0,1,2,3,4;m=1,0,1,2)の電子的性質の評価 (2009)
  • Author(s): 亀尾 肇、望月信介、伊藤 大、上原直樹、藤本順子、鈴木寛治
  • Organizer: 日本化学会春季年会
  • Place of Presentation: 千葉
  • Year and Date: 2009-03-29
• [Presentation] Activation of Nitrogen-Hydrogen Bonds of Ammonia Induced by Trinuclear Polyhydrido Clusters Containing Ruthenium and Osmium (2008)
  • Author(s): 亀尾 肇、中島裕美子、鈴木寛治
  • Organizer: 有機金属化学討論会
  • Place of Presentation: 大阪
  • Year and Date: 2008-09-29
• [Presentation] Reaction of Ru-Os Heterobimetallic Complex (C5Me5)Os(μ-H)4Ru(C5Me5) with tert-Phosphine (2008)
  • Author(s): Kameo, H.; Suzuki, H.
  • Organizer: The 23th International Conference on Organometallic Chemistry
  • Place of Presentation: Rennes
  • Year and Date: 2008-07-17
• [Presentation] Ru5M骨格を有する六核ポリヒドリドクラスターの合成と構造 (2008)
  • Author(s): 望月信介, 高尾俊郎, 鈴木寛治
  • Organizer: 日本化学会第88回春季年会
  • Place of Presentation: 立教大学
  • Year and Date: 2008-03-28
• [Presentation] ルテニウムとオスミウムを含む二核テトラヒドリド錯体と産休ホスフィンとの反応における異種金属効果 (2008)
  • Author(s): 亀尾肇, 鈴木寛治
  • Organizer: 日本化学会第88回春季年会
  • Place of Presentation: 立教大学
  • Year and Date: 2008-03-27
• [Presentation] ルテニウムとオスミウムを含む二核テトラヒドリド錯体と三級ボスフィンとの反応における異種金属効果(2E8-49) (2008)
  • Author(s): 亀尾肇, 鈴木寛治
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 立教大学
  • Year and Date: 2008-03-27
• [Presentation] Reaction of Ru-Os Heterobimetallic Complex (C5Me5)Os(・-H)4Ru(C5Me5) with tert-Phosphine (2008)
  • Author(s): 亀尾 肇、鈴木寛治
  • Organizer: International Conferens on Organometallic Chemistry
  • Place of Presentation: Rennes
• [Presentation] Reaction of Tetra-nuclear Polyhydrido Complexes of Ruthenium with Molecular Oxygen: Mono- or Dioxygenation? (2007)
  • Author(s): Kameo, H.; Ohki, Y.; Suzuki, H.
  • Organizer: 第54回有機金属化学討論会
  • Place of Presentation: 広島大学
  • Year and Date: 2007-10-28
• [Presentation] Reaction of Tetra-Nuclear Polyhydrido Complexes of Ruthenium with Molecular Oxygen: Mono-or Dioxygenation? (PA-234) (2007)
  • Author(s): Hajime Kameo, Yasuhiro Ohki, Hiroharu Suzuki
  • Organizer: 第54回有機金属化学討論会
  • Place of Presentation: 広島大学
  • Year and Date: 2007-10-28
• [Presentation] ルテニウムおよびオスミウムから成る三核ポリヒドリド錯体の合成-それらのμ_3オキソ誘導体とアンモニアとの反応(2B5-35) (2007)
  • Author(s): 亀尾肇, 島隆則, 鈴木寛治
  • Organizer: 日本化学会 第1回関東支部大会
  • Place of Presentation: 首都大学東京
  • Year and Date: 2007-09-28
• [Presentation] 架橋ヒドリド配位子を含むルテニウムータングステン系クラスターによる触媒的ラジカル反応(2D-08) (2007)
  • Author(s): 松宮史宜, 大石理貴, 鈴木寛治
  • Organizer: 第57回 錯体化学討論会
  • Place of Presentation: 名古屋工業大学
  • Year and Date: 2007-09-26
• [Presentation] 6族遷移金属とルテニウムを含む異種金属クラスター上での炭化水素への官能基導入 (2007)
  • Author(s): 市川利明, 伊藤淳一, 鈴木寛治
  • Organizer: 第100回触媒討論会
  • Place of Presentation: 北海道大学
  • Year and Date: 2007-09-19
• [Presentation] 6族遷移金属とルテニウムを含む異種金属クラスター上での炭化水素配位子への官能基導入(3J31) (2007)
  • Author(s): 市川利明, 伊藤淳一, 鈴木寛治
  • Organizer: 第100回 触媒討論会
  • Place of Presentation: 北海道大学
  • Year and Date: 2007-09-19
• [Presentation] Cleavage of N-H Bonds of Ammonia Induced by Polyhydrido Clusters (2007)
  • Author(s): Kameo, H.; Nakajima, Y.; Suzuki, H.
  • Organizer: The 14th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
  • Place of Presentation: 奈良
  • Year and Date: 2007-08-03
• [Remarks]
  • URL: http://www.apc.titech.ac.jp/~hsuzuki/index.html
• [Remarks] ホームページ
  • URL: http://www.apc.titech.ac.jp/~hsuzuki/index.html