Development of Catalytic Reactions Promoted by Ruthenium Complexes Having a Multidentate Silyl Ligand

2009 Fiscal Year Final Research Report

• Project/Area Number: 20750040
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Inorganic chemistry
• Research Institution: Tohoku University
• Principal Investigator: KOMURO Takashi Tohoku University, 大学院・理学研究科, 助教 (20396419)
• Project Period (FY): 2008 – 2009
• Keywords: シリル錯体 / ルテニウム錯体 / 触媒反応 / 配位不飽和錯体 / 多座配位子 / キレート配位子 / ヒドロシリル化 / C-H結合活性化

Research Abstract

As a development of a new hydrosilylation reaction catalyzed by a 16-electron bis(silyl)ruthenium complex A, in which phenyl-substituted alkyne reacts with tertiary silane to give (E)-alkene having a silylated aromatic group, we got the following results (1)-(3). (1)This reaction for various combinations of alkynes and silanes was investigated to elucidate the substituent effect of the substrates on the hydrosilylation. (2)Complex A was found to become a catalyst for hydroboration of an alkyne C≡C triple bond. (3)Related complexes having an N-heterocyclic carbene ligand instead of the phosphine ligand in A were synthesized. Comparison of their catalytic activity on the hydrosilylation revealed how the difference of the ligand influenced on the reactivity.

Research Products

• [Journal Article] Thermal reaction of a ruthenium bis(silyl) complex having a lutidine-based Si, N, Si ligand: formation of aμ-silyl(μ-silylene) diruthenium complex involving a 3c-2e Ru-Si-C interaction (2010)
  • Author(s): T. Komuro, H. Tobita
  • Journal Title: Chem. Commun. 46 Pages: 1136-1137
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization ofκ2C, N-N-Silyliminoacyl Tungsten Complexes Cp*(CO)2W{κ2C, N-C(R)=NSiR´3} [R = Me, Et, i-Pr, t-Bu; R´3 = (p-Tol)2Me, (p-Tol)3, Et3; Cp* =η5-C5Me5]: Thermally Induced Carbon-Carbon Bond Cleavage of Their Iminoacyl Ligands (2010)
  • Author(s): E. Suzuki, T. Komuro, Y. Kanno, M. Okazaki, H. Tobita
  • Journal Title: Organometallics 29 Pages: 1839-1848
  • Peer Reviewed
• [Journal Article] Synthesis and Structures of Alkynylchlorocyclotriphosphazenes and Their Cluster-forming Reactions with Octacarbonyldicobalt (2009)
  • Author(s): T. Komuro, K. Mori, H. Tobita
  • Journal Title: Heterocycles 77 Pages: 1171-1183
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of DMAP-Stabilized Aryl(silylene) Complexes and (Arylsilyl)(DMAP) Complexes of Tungsten: Mechanistic Study on the Interconversion between These Complexes via 1, 2-Aryl Migration (2009)
  • Author(s): E. Suzuki, T. Komuro, M. Okazaki, H. Tobita
  • Journal Title: Organometallics 28 Pages: 1791-1799
  • Peer Reviewed
• [Journal Article] New Hydrosilylation Reaction of Arylacetylene Accompanied by C-H Bond Activation Catalyzed by a Xantsil Ruthenium Complex (2008)
  • Author(s): H. Tobita, N. Yamahira, K. Ohta, T. Komuro, M. Okazaki
  • Journal Title: Pure Appl. Chem. 80 Pages: 1155-1160
  • Peer Reviewed
• [Journal Article] Recombination of an Fe-Si-P Linkage to an Fe-P-Si Linkage through an Isolable Intermediate Phosphasilaferracyclopropane (2008)
  • Author(s): M. Okazaki, T. Yoshitomi, J. Naito, A. Sato, T. Komuro, H. Tobita
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 17674-17675
  • Peer Reviewed
• [Remarks]
  • URL: http://inorg.chem.tohoku.ac.jp/