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The Chemistry of Linkages between Main Group Elements and Transition Metals

Research Project

Project/Area Number 09239105
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionOSAKA CITY UNIVERSITY

Principal Investigator

OZAWA Fumiyuki  Osaka City University, Professor, 工学部, 教授 (40134837)

Co-Investigator(Kenkyū-buntansha) MIYAURA Norio  Hokkaido University, Professor, 大学院・工学研究科, 教授 (10002049)
TATSUMI Kazuyuki  Nagoya University, Professor, 物資科学国際研究センター, 教授 (10155096)
SAKAKI Shigeyoshi  Kumamoto University, Professor, 工学部, 教授 (20094013)
OSAKADA Kohtaro  Tokyo Institute of Technology, 資源化学研究所, 教授 (00152455)
TOBITA Hiromi  Tohoku University, Asso.Professor, 大学院・理学研究科, 助教授 (30180160)
Project Period (FY) 1997 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥89,500,000 (Direct Cost: ¥89,500,000)
Fiscal Year 1999: ¥30,500,000 (Direct Cost: ¥30,500,000)
Fiscal Year 1998: ¥30,000,000 (Direct Cost: ¥30,000,000)
Fiscal Year 1997: ¥29,000,000 (Direct Cost: ¥29,000,000)
KeywordsMain group element-transition metal bond / Boron / Group 14 elements / Chalcogen atoms / Oxidative addition / Reductive elimination / Insertion / Transmetallation / ボウ素 / ケイ素 / ゲルマニウム / スズ / リン / イオウ / 遷移金属 / 錯体 / ジシリル錯体 / シリレン錯体 / ジボリル錯体 / スルフィド錯体 / 金属クラスター / ヒドロシリル化反応 / シリル錯体 / ゲルミル錯体 / ボリル錯体 / ジシリル化反応 / ジボリル化反応
Research Abstract

The following six subjects have been explored to establish new basic concepts for chemical bonding between main group elements and transition metals.
(1) Saturated Linkages between Main Group Elements and Transition Metals (F.Ozawa). A series of platinum (II) complexes bearing alkyl, silyl, germyl, and stannyl ligands have been prepared, and their structures and reactivities towards alkyne-insertion and reductive elimination have been examined by X-ray diffraction analysis, NMR spectroscopy, and kinetic experiments.
(2) Theoretical Study of the Reactions between Transition Metal Complexes and Inter-element Linkages (S.Sakaki). Oxidative addition of Si-B, Si-C, and Si-Si bonds towards a platinum (0) or palladium (0) complex has been examined by means of ab initio MO methods. The reactions of Si-C and Si-Si bonds proceed via an unusual non-planar transition state.
(3) Bonding and Reactions Characteristics of Early Transition Metal Chalcogenides (K.Tatsumi). A series of mononuclear, group 6 … More metal chalcogenides have been synthesized by the use of C-Y bond cleaving reactions. The resulting Cp^*MY_3 type complexes (Y=O, S, Se) serve as versatile building blocks of transition metal clusters.
(4) Transition Metal-catalyzed Reactions of Diborons (N.Miyaura). Transition-metal catalyzed activation of diboron compounds is an efficient way of synthesizing organoboron compounds which are versatile intermediates in organic synthesis. The reactions include diboration of unsaturated hydrocarbons, cross-coupling between diborons and organic halides, and conjugate addition of organoboronic acids to enones.
(5) Unsaturated Linkages between Main Elements and Transition Metals (H.Tobita). Base-stabilized silylene complexes have been prepared with a variety of late transition metals including rhodium, iridium, iron, and ruthenium, and a systematic study has been carried our for their structures and reactions. Some of the complexes undergo cycloaddition with C=O and C=N double bonds.
(6) Transmetallation of Thiolate and Silyl Ligands (K.Osakada). Mechanistic details of the title reaction have been gained by X-ray diffraction analysis of intermediates and reaction kinetics. A μ-silyl complex of dirhodium is a remarkable example. Less

Report

(4 results)
  • 2000 Final Research Report Summary
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (57 results)

All Other

All Publications (57 results)

  • [Publications] Y.Maruyama: "Mechanisms of C-Si and C-H Bond Formation on the Reactions of Alkenylruthenium (II) Complexes with Hydrosilanes"Organometallics. 19. 1308-1318 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohmura: "Rhodium-or Iridium-Catalyzed trans-Hydroboration of terminal Alkynes, Giving (Z)-1-Alkenylboron Compounds"J.Am.Chem.Soc.. 122. 4990-4991 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.-J.Kim: "Dipalladium Complexes with Bridigng Diorganosilyl Ligands.Synthesis,Structures,and Properties of [LPd(μ-SiH(R)Ph)]_2(R=Ph,Me;L=PMe_3,PEt_3,PMePh_2)"J.Chem.Soc., Dalton Trans.. 2000. 471-422 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Sakaki: "Theoretical Study on σ-Bond Activation of (HO) _2B-XH_3 by M (PH_3)_2 (X=C,Si,Ge,or Sn ; M=Pd or Pt)"Organometallics. 18. 4825-4837 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Arikawa: "Synthesis of Bis{(2-dimethylphosphino)ethane-1-thiolato}bis(t-butylthiolato)-Molybdenum (IV) and Its Cluster Forming Reactions with FeCl_2 and CuBr"Inorg.Chem.. 38. 4549-4553 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] H.Tobita: "Synthesis and Properties of Intramolecularly Base-Stabilized Disilanyl (silylene) ruthenium and -iron Complexes"Organometallics. 17. 2850-2856 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Maruyama, et al.: "Mechanisms of C-Si and C-H Bond Formation on the Reactions of Alkenylruthenium (II) Complexes with Hydrosilanes"Organometallics. 19. 1308-1318 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohmura, et al.: "Rhodium-or Iridium-Catalyzed trans-Hydroboration of terminal Alkynes, Giving (Z)-1-Alkenylboron Compounds"J.Am.Chem.Soc.. 122. 4990-4991 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.-J.Kim, et al.: "Dipalladium Complexes with Bridigng Diorganosilyl Ligands. Synthesis, Structures, and Properties of [LPd (μ-SiH (R) Ph]_2 (R=PH, Me ; L=PMe_3, PEt_3, PMePh_2)"J.Chem.Soc., Dalton Trans.. 471-422 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Sakaki, et al.: "Theoretical Study on s-Bond Activation of (HO)_2B-XH_3 by M(PH_3)_2 (X=C, Si, Ge, or Sn ; M=Pd or Pt)"Organometallics. 18. 4825-4837 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Arikawa, et al.: "Synthesis of Bis {(2-dimethylphosphino) ethane-1-thiolato} bis (t-butylthiolato)-Molybdenum (IV) and Its Cluster Forming Reactions with FeCl_2 and CuBr"Inorg.Chem.. 38. 4549-4553 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] H.Tobita, et al.: "Synthesis and Properties of Intramolecularly Base-Stabilized Disilanyl (silylene) ruthenium and -iron Complexes"Organometallics. 17. 2850-2856 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] F. Ozawa: "Reactions of bis (silyl) palladium (II) cpmplexes with allyl halides. Synthesis of mono (silyl) palladium (II) halides and X-ray structure of trans PdCL(SiF_2Ph) (Pme_2PH)_2"Inorg. chim. Acta. 296. 19-25 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] F. Ozawa: "A New Process for C-Si Bond Formation from cis-Alkyl (silyl) platinum(II) Complexes"Chem. Lett.. (12). 1289-1290 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] F. Ozawa: "Insertion of Phenylacetylene into cis-Silyl (stannyl) platinum Complexes"Chem. Lett.. (12). 1307-1308 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Y. Maruyama: "Mechanisms of C-Si and C-H Bond Formation on the Reactions of Alkenylruthenium (II) Complexes with Hydrosilanes"Organometallics. 19(印刷中). (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] K. Hasebe: "Thermolysis Reactions of cis-PtR (SiPH^3) (Pme_2PH)_2 in Solution"Organometallics. 19(印刷中). (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] Y. Maruyama: "Hydrosilylation of 1,4-bis (trimethylsilyl)-l-buten-3-ynes using late transition metal hydrides as catalyst precursors"J. Organomet. Chem. (印刷中). (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] B. Biswas: "Theoretical Study of the Structure, Bonding Nature, and Reductive Elimination Reaction of Pd (XH_3) (η^3-C_3H_5)(PH _3)(X=C, Si, Ge, Sn)"Organometallics. 18. 4015-4026 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] S. Sakaki: "Theoretical Study on σ-Bond Activation of (HO)_2 B-XH_3 by M (PH_3)_2(X=C, Si, Ge, or Sn; M=Pd or Pt)"Organometallics. 18. 4825-4837 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] S. Sakaki: "Pt-catalyzed hydrosillylation of ethylene. A theoretical study of the reaction mechanism"Coord. Che m. Rev.. 190-192. 933-960 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] J.-P. Lang: "Aggregation of the Half-sandwich Trisulfido Complex of Tungsten with Silver Ions : Synthesis of Cyanide-bridged Helical Polymer"Irorg. Chem.. 38. 1364-1367 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Y. Arikawa: "Synthesis of Bis {2-dimethylphosphino) ethane-l-thiolato} bis (t-butylthiolato) - Molybdenum (IV) and Its Cluster Forming Reactions with FeCl_2and CuBr"Irorg. Chem.. 38. 4549-4553 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] J-P. Lang: "Novel W/Cu/S Cluster Compounds Derived from [PPh_4][η^5-C_5Me_5(WS_3] : Synthesis and Structures of a Triple Incomplete Cubane Cluster"Chem. Commun. 2315-2316 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K. Takahashi: "Synthesis of l-Alkenylboronic Esters via Palladium-catalyzed Cross-coupling Reaction of Bis (pinacolato) diboron with l-Alkenyl Halides and Triflates"Chem. Lett.. 126-127 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] T. Ishiyama: "Platinum (0)-Catalyzed Diboration of Methylenecyclopropanes with Bis (pinacolato)- diboron : A Selective Route to 2,4-Bis (boryl)-l-butenes"Synlett.. 1790-1792 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] H. Tobita: "Extremely Facile Arene Exchange on a Ruthenium (II) Complex Having a Novel Bis (silyl) Chelata Ligand (9,9-Dimethylxanthene-4,5-diyl) bis (dimethylsilyl) (Xantsil)"Organometallics. 18. 2058 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K. Kuge: "Synthesis and Structures of Heterometallic Clusters [CpFe (CO)_2]_2(μ^3-S_2W (CO)_5and Cp_2Fe_2 (CO)_2(μ CO) W^3-S) W (CO)_5 and Kinetic Study of Migration Study of Migration"Chem, Commun.. (12). 1061-1062 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Y. -J. Kim: "Dipalladiium Complexes with Bridigng Diorganosilye Ligands. Synthesis, Structures, and Properties of [Lpd (μ-SiH (R) Ph)]_2(R=Ph, Me ; L=Pme_3, Pet_3,PMePh_2"J. Chem. Soc, Delton Trans.. (3). 417-422 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] K, Osakada: "Mechanistic Features of Intermoleculae Thiolato Ligands Trasfer from Thiolatotitanocene to Pt (Cl) Me (cod) To Give Methyl (arylthiolato) platinum (II) Complexes"Bull. Chem. Soc. Jpn. 73(印刷中). (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] 丸山洋一郎: "Reactions of Alkenylruthenium(II)Complexes with Hydrosilane:C-Si vs C-H Bond Formation" Chemistry Letters. (9). 905-906 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 片山博之: "Convenient Routes to Vinylideneruthenium Dichlorides with Basic and Bulky Tertiary Phosphine Ligands(PPri_3 and PCy_3)" Organometallics. 17(23). 5190-5196 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 小澤文幸: "Mechanistic Study on the Insertion of Phenylacetylene into cis-Bis(silyl)platinum(II)" Organometallics. 17(26). 5630-5639 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 榊 茂好: "A Theoretical Study of the C-H Activation of Methane Derivatives. Significant Effects of Electron-withdrawing Substituents" Organometallics. 17(7). 1278-1289 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 榊 茂好: "Theoretical Study of Platinum(0)-Catalyzed Hydrosilylation of Ethylene. Chalk-Harrod Mechanism or Modified Chalk-Harrod Mechanism" Organometallics. 17(12). 2510-2523 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 榊 茂好: "Is a Transition State Planar or non-Planar in Oxidative Additions of C-H,Si-H,C-C,and Si-C Bonds to Pt(PH_3)_2 ? A Theoretical Study" Journal of Physical Chemistry. 102(41). 8027-8036 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 川口博之: "Mono(pentamethylcyclopentadienyl)tantalum Complexes Cotaining a Structurally Versatile Enediamido(2-)Ligand" Organometallics. 17(20). 4380-4386 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] J.-P.Lang: "Low Temperature Solid State Reactions of(NH_4)_2[MS_4](M=W,Mo) with[Cu(CH_3CN)_4](PF_6)and CuBr in the Presence of Bis(diphenylphosphino)metahne(dppm)" Inorganic Chemistry. 37(24). 6308-6316 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 杉山浩康: "Synthesis of Alkynethiolato and Alkyneselenolato Complexes of Titanocene(IV)and Samarocene(III)" Inorganic Chemistry. 37(26). 6773-6779 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 石山竜生: "Platinum(0)-Catalyzed Diboration of Allenes with Bis(pinacolato)diboron" Tetrahedron Letters. 39. 2357-2360 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 高谷佳輝: "Rhodium-Catalyzed Asymmetric 1,4-Addition of Aryl- and 1-Alkenylboronic Acids to Enones" Journal of the American Chemical Society. 120(22). 5579-5580 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 酒井正明: "Rhodium-Catalyzed Addition of Organoboronic Acids to Aldehydes" Angew.Chem.Int.Ed.Engl.37. 3279-3281 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 岡崎雅明: "Thermal Reactions of Alkyl(hydrido)(hydrosilyl)iridium(III)Complexes:Generation of a Hydrido(silylene)iridium(I)Species via the Reductive Elimination" Jounal of Organometallic Chemistry. 553. 1-13 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 飛田博実: "Synthesis,Structure,and Reactivity of a Bis(silylene)(carbonyl)ruthenium Complex and a Novel Addition Reaction of Photochemically Generated Dimethylsilylene to Bis(silylene)Complexes" Orgsnometallics. 17(3). 2844-2849 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 飛田博実: "Synthesis and Properties of Intramolecularly Base-Stabilized Disilanyl(silylene)ruthenium and-iron Complexes" Organometallics. 17(3). 2850-2856 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 丸山洋一郎: "Regio- and Stereoselective Hydrosilylation of 1,4-Bis(trimethylsilyl)-3-buten-1-ynes" Chem.Lett.(7). 623-624 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 丸山洋一郎: "Mechanistic Study of Ruthenium-catalyzed Hydrosilation of 1-Trimethylsilyl-1-buten-3-yne" J.Am.Chem.Soc.120(7). 1421-1429 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] 小澤文幸: "Kinetic Studies on the Reductive Elimination of cis-PtMe(SiPh_3)(PMe_2Ph)_2and cis-PtMe(GePh_3)(PMe_2Ph)_2" Organometallics. 17(6)(未定). (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] 榊 茂好: "Oxidative Addition of a C-H σ Bond to M(PH_3)_2(M=Pd or Pt).An ab initio Molecular Orbital Study on the Chelate Phosphine Effect" J.Chem.Soc.Dalton Trans.(3). 803-809 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 榊 茂好: "A Theoretical Study of Platinum-Catalyzed Disilylation of Alkene" J.Organomet.Chem.535(イ). 25-28 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 石山 竜生: "Diboration of Alkenes with Bis(pinacolato)diboron Catalysed by a Platinum(0)Complex" Chem.Commun.(7). 689-690 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 石山竜生: "Synthesis of Arylboronates via the Palladium(0)-Catalyzed Cross-Coupling Reaction of Tetra(alkoxo)diborons with Aryl Triflates" Tetrahedron Lett.38(19). 3447-3450 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 安彦崇昭: "A Sequence of Palladium-Catalyzed Borylation of Allyl Acetates with Bis(pinacolato)diboron and Intramolecular Allylboration for the Cyclization" Chem.Lett.(8). 811-812 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 和田裕明: "Reactivity of a Donor-Stabilized Bis(silylene)ruthenium Complexes toward Nucleophiles ROH(R=Me,H)" Organometallics. 16(10). 2200-2203 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Lung-Shiang Luh: "Synthesis and Properties of σ-Alkyl-Substituted Silanediyl-Bridged and Silanetriyl-Bridged Diiron Complexes" Bull.Chem.Soc.Jpn.70(9). 2193-2200 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 飛田博実: "Reaction of Silyl(carbonyl)iron Complexes with LiAlH_4 Giving Methylsilanes:Reduction of a Carbonyl Ligand and Coupling with a Silyl Group" Chem.Lett.(8). 805-806 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 和田 裕明: "Intramolecular Aromatic C-H Bond Activation by a Silylene Ligand in a Methoxy-Bridged Bis(silylene)Ruthenium Complex" Organometallics. 16(18). 3870-3872 (1997)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2019-02-15  

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