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2000 Fiscal Year Final Research Report Summary

Development of Selective Organic Synthesis and Catalysis Based on Characteristics of Organotransition Compounds

Research Project

Project/Area Number 09309006
Research Category

Grant-in-Aid for Scientific Research (A).

Allocation TypeSingle-year Grants
Section一般
Research Field 広領域
Research InstitutionOsaka University

Principal Investigator

TANI Kazuhide  Osaka University, Graduate School of Engineering Science, Professor, 基礎工学研究科, 教授 (60029444)

Co-Investigator(Kenkyū-buntansha) YAMAGATA Tsuneaki  Osaka University, Graduate School of Engineering Science, Research Associate, 基礎工学研究科, 助手 (70166594)
KATAOKA Yasutaka  Osaka University, Graduate School of Engineering Science, Lecturer, 基礎工学研究科, 講師 (90221879)
MASHIMA Kazushi  Osaka University, Graduate School of Engineering Science, Associate Professor, 基礎工学研究科, 助教授 (70159143)
Project Period (FY) 1997 – 2000
Keywordsiridium / rhodium / tantalum / P-N ligand / stereospecific methyl migration / C-H activation / O-H activation / MMA polymerization
Research Abstract

With the aim of discovering new organic synthesis and catalysis based on characteristics of organotransition metal compounds we performed the research project. The following new results were obtained.
1) Neutral iridium diphosphine complexes carrying peraryldiphosphines, [IrCl (diphosphine)]_2, can activate easily O-H bonds of alcohol, water, etc to produce their oxidative addition products. The complex is an efficient catalyst for transfer hydrogenation of unsaturated compounds using methanol as a hydrogen donor.
2) Low valent vanadium(II) compounds are useful reagents for selective alkylation, allylation, C-C bond formation accompanying C-O bond cleavage of carbonyl compounds.
3) General method of preparation of complexes Tp^*MCl_nL_O {Tp^*=hydrotris (pyrazolyl) borates, M=group 4-6 transition metal} using Tp^*SnR_nCl_<3-n> (R=alkyl) as a Tp^* transfer reagent was provided
4) New optically active Cp'-P ligands, containing both an indenyl group carrying an optically active substituent and … More a diphenylphosphino group connected by an alkylene spacer, were synthesized and their stereoselective rhodium complexes regulating the panar as well as the central chirality were prepared. A theoretical catalytic cycle for selective formation of α, β-unsaturated ketones from acetylene, CO, methyl iodide and trimethyl aluminum with (Cp'-P)Rh(CO) as a catalyst was established.
5) A coordinatively flexible P-N ligand which has a diphenylphosphino group and a 2-pyridyl group connected by an oxaalkylene chain was synthesized. Direct observation of reversible oxidative addition and reductive elimination of C(sp^3)-H bonds was accomplised by using the iridium complexes of the P-N ligand.
6) A series of 1,4-diazadiene complexes of niobium and tantalum have been prepared. These complexes becom active catalysts for polymerization of MMA.By choosing ancillary ligands, 1,4-diazadiene can coordinate to a metal in several different coordination geometry, planar σ^2-, prone and supine nonplanar σ^2, π-enediamide. Tacticity and polydispersity of PMMA could be regulated. Less

  • Research Products

    (50 results)

All Other

All Publications (50 results)

  • [Publications] 片岡靖隆: "Direct Construction of Quaternary Carbons from Carbonyl Compounds Utilizing Low-Valeut Vanadium Complexes"Tetrahedron. 53巻. 9525-9540 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 真島和志: "Tp^*Sn (Cl) Bu_2 as a Convenient Reagent for the Preparation of Hydrotris (3,5-dimethylpyrazolyl)borate Complexes of Niobium,Tantalum, and Zirconium"Organometallics.. 16巻. 2760-2762 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 山縣恒明: "Preparation, Properties, and Structures of [IrCl (diphosphine)]_2(diphosphine=(R)-BINAP and BPBP)"Chem.Lett. 1215-1216 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 片岡靖隆: "A NovelC-C Single Bond Formation Accompanying C-O Bond Cleavage by Use of Ketone, an Alkylating Reagent, and a Low-valent Vanadium Complex in the Presence of a Catalytic Amount of Molecular Oxygen"J.Org.Chem.. 62巻. 8109-8113 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 片岡靖隆: "Stabilizing Effect of HMPA (Hexamethylphosphoric Triamide) on Vanadium-CarbonBonds and Their Application to Carbon-Carbon Bond Formation Reactions"Organometallics. 16巻. 4788-4795 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 片岡靖隆: "Generation of Versatile Reagents Derived from R_2Zn and a Vanadium (III) or a Vanadium (IV) Complex and Their Application to Organic Synthesis"J.Org.Chem.. 24巻. 8540-8543 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 真島和志: "Theoretical stnfies of Multiple Meteal-Metal Bonds between Divalent Molybdenum Ions in Dimers, Tetramera, and Clusters"Ball.Chem.Soc.Jpn.. 71. 99-112 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 真島和志: "1,8-Diphenylocta-1,3,5,7-teiraene Complexes of Ruthenium (II) : Crystal Structures of [μ-(s-cis-1,2,3,4-η ; s-cis-5,6,7,8-ηPhCH=CHCH=CHCH=CH-CH=CHPh) (RuClCp^*)_2] and [μ-(s-trans-1,2,3,4-η : s-trans-5,6,7,8-η-PhCH=CHCH=CHCH=CHCH=CHPh) {Ru(acac)_2} _2]"Organometallics. 17. 410-414 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 真島和志: "Unique Complexation by the Tridentate Ligands, 6-Diphenylphosphino-2-pyridonate (pyphos) and 6-Diphenylphosphino-2-pyridone (pyphosl I), on Ruthenium (II) : Crystal Structures of (pyphosl I) RuCl (μ-Cl) Mo_2Cl (pyphos)_3, RuCl-(CO)(pyphosl I)_2, [Ru (pyphos)_3] (μ-Na)_2 [Ru (Ryphos)_3"Inorganica Chimica Acta (Bioinorg.Chem.). 270. 459-466 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 谷一英: "Reductive dimerization of dialkyl acetylenedicarboxylate catalyzed by [Rh (binap)-(MeOH)_2 ClO_4 in Methanol"J.Organomet.Chem.. 560. 253-255 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 真島和志: "Polymerization of methyl methacrylate catalyzed by tantalum-diene complexes,Ta(η^5-C_5R_5) (η^4-1,3-butadiene)_2 (R=H and Me), in the presence of cocatalyst AlMe(OC_6H_2-2,6-(^tBu)_2-4-Me)_2"Proc.Japan Acad.. 74,SerB. 217-220 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 片岡靖隆: "Hight Diastereoselectiv Oxidative Addition of Aikyl Halides to Rhodium and Iridium Carbonyl Complexes Having an η^5 : η^1-(Ind-P)_n Ligand((Ind-P)_nH=C_9H_7-(CH_2)PR_2 ; R=Ph, Cy ; n=2-4)"Organometallics. 17. 4338-4340 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 真島和志: "The Half-sandwich Hydride and 16-Electron Complexes of Rhodium and Iridium Containing (1S,2S)-N-(p-Toluenesulfonyl)-1,2-diphenylethylenediamine : Relevant to the Asymmetric Transfer Hydrogenation"Chem.Lett.. 1201-1202 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 谷一英: "Facile Oxidative Addition of O-H Bonds of Methanol and Water to Ir^I Complexes HavinPeraryldiphoshine Ligands : Isolation and Characterization of Hydrido (methoxo)-and Hydrido (hydroxo) complexes of Ir^<III>"Angew.Chem.Internat.Ed.Engl.. 37巻. 3381-3383 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 谷一英: "Efficient Transfer Hydrogenation of Alkynes and Alkenes with Methanol Catalysed by Hydrido (methoxo) iridium (III) Complexes"Chem.Commun.. 1821-1822 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 真島和志: "Unique Complexation of 1,4-Diaza-1,3-butadiene Ligand on Half-metallocene Fragments of Niobium and Tantalum"Organometallics. 18巻. 1471-1481 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 片岡靖隆: "Third Generation of the Cp'-P Ligand : Highly Stereoselective Control of Central Chirality Arising at a Metal Center"Organometallics. 18巻. 5423-5425 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 谷一英: "有機遷移金属錯体反応活性種の開発とその選択的有機合成への応用"生産と技術. 52巻. 39-44 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 真島和志: "1-Aza-1,3-butadiene Complexes of Tantalum : Preparation and Alkylation of TaCl_2(η^5-C_5Me_5)(η^4-1-aza-1,3-butadieue)"Journal Organometallic Chemistry. 593〜594巻. 69-76 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 片岡靖隆: "Configurationally Stable Metal-centered Chirality : Stereospecific and Regioselectiv Rhodaacylation of Alkynes Controlled by the Third Generation of the [Cp'-P] H Ligand"Chemical Communications. 841-842 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 押木俊之: "Substituent Effect on Organotin Tp^* Compounds as the Tp^* Reagent for the Preparation of Mono Tp^* Complexes of Group 4-6 Metals (Tp^*=Tris (3,5-dimethylpyrazol-1-yl) hydroborate)"Bulletin Chemical Society of Japan. 73巻. 1735-1748 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 真島和志: "Convenient Synthesis of Anionic Dinuclear Ruthenium (II) Complexes [NR_2H_2] 〔{(RuCl(diphosphine)}_2 (μ-Cl)_3〕〔diphosphine=2,2'-bis (diphenyl-phosphino)-1,1'-binaphthyl,2,2'-bis (di(p-toly) phosphino)-1,1'-binaphthyl, and 1,2-bis(diphenyl-phosphino) benzene〕 : Crystal Structure of 〔NEt_2H_2〕〔{RuCl(1,2-bis(diphenylphosphino)-benzene)}_2(μ-Cl)_3〕"Journal Organometallic Chemistry. 607巻. 51-56 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 松尾豊: "Synthesis and Characterization of Bis (iminopyrrolyt) zirconinm Complexes"Chemistry Letters. 1114-1115 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 田中光洋: "Unique Axial Interaction of a Quadruply-Bouded Cr(II)=Cr(II) with Two Pt(II) Atoms in the Linearly Aligned pt-Cr-Cr-Pt Supported by Four 6-Diphenylphosphino-2-pyridonate Ligands"Bulletin Chemical Society of Japan. 73巻. 67-75 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 片岡靖隆: "Acetonitrile Accelerated Stcrcosetective C-H Bond Activation of the Cationic Ir(I) Complex Having the PN/CH_3 Heterochelate Hyrid Ligand"Chemistry Letters. 印刷中. (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 松尾豊: "Half-Metaliocene Tantalum Complexes Bearing Methyl Methacrylate (MMA) and 1,4-Diaza-1,3-diene Ligands as MMA Polymerization Catalysts"Angewandte Chemie International Edition. 40巻. (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 谷一英: "Isomerization of Olefin and the Related Reactions"Transition Metals for Organic Synthesis : Building Blocks and Fine Chemicals ed. by M.Beller and C.Bolm, Vol 1,Chapter 2.9, pp147-157, Wiley-VCH,Weinheim,1998.. 10 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 真島和志: "Living Polymerization Catalyzed by Transition Metal Complex"Ring-opening Metathesis Polymerization Catalyzed by Tantalum Complexes (in Japanese).. 24 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 谷一英: "廣川 有機薬科学実験講座 第2巻 創薬化学の基礎となる不斉反応"廣川書店. 18 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 谷一英: "Catalytic Heterofunctionalization"Wiley-VCH (印刷中). (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Kataoka, I.Makihira, H.Akiyama, and K.Tani: "Direct Construction of Quaternary Carbons from Carbonyl Compounds Utilizing Low-Valent Vanadium Complexes"Tetrahedron. 53. 9525-9540 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Mashima, Y.Matsuo, and K.Tani: "Nonplanar σ^2, π-and Planar σ^2 Enediamide Coordinations of 1,4-Di(p-methoxyphenyl)-1, 4-diaza-1, 3-butadiene (=MeOC_6H_4-DAD) on Ta(η^5-C_5R_5) Fragments (R=H, Me) : Crystal Structures of TaCl_2(σ^2, π-MeOC_6H_4-dad)(η^5-C_5H_5) and Ta(σ^2-MeOC_6H_4-dad)(η^5-C_5Me_5)(η^4-1,3-butadiene)"Chem.Lett.. 767-768 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Mashima, T.Oshiki, and K.Tani: "Tp^*Sn(CI)Bu_2 as a Convenient Reagent for the Preparation of Hydrotris(3,5-dimethylpyrazolyl)borate Complexes of Niobium, Tantalum, and Zirconium"Organometallics. 16. 2760-2762 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Yamagata, A.Iseki, and K.Tani: "Preparation, Properties, and Structures of [IrCl(diphosphine)]_2 (diphosphine=(R)-BINAP and BPBP)"Chem.Lett.. 1215-1216 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Kataoka, H.Akiyama, I.Makihira, and K.Tani: "A Novel C-C Single Bond Formation Accompanying C-O Bond Cleavage by Use of Ketone, an Alkylating Reagent, and a Low-valent Vanadium Complex in the Presence of a Catalytic Amount of Molecular Oxygen"J.Org.Chem.. 62. 8109-8113 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Kataoka, I.Makihira, T.Yamagata, and K.Tani: "Stabilizing Effect of HMPA (Hexamethylphosphoric Triamide) on Vanadium-Carbon Bonds and Their Application to Carbon-Carbon Bond Formation Reactions"Organometallics. 16. 4788-4795 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Kataoka, I.Makihira, M.Utsunomiya, and K.Tani: "Generation of Versatile Reagents Derived from R_2n and a Vanadium(III) or a Vanadium(IV) Complex and Their Application to Organic Synthesis"J.Org.Chem.. 24. 8540-8543 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Tani, K.Ueda, K.Arimitsu, T.Yamagata, Y.Kataoka: "Reductive Dimerization of Dialkyl Acetylenedicarboxylate Catalyzed by [Rh(binap)(MeOH)_2] ClO_4 in Methanol"J.Organomet.Chem.. 560. 253-255 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Kataoka A.Shibahara, Y.Saito, T.Yamagata, and K.Tani: "Highly Diastereoselective Oxidative Addition of Alkyl Halides to Rhodium and Iridium Carbonyl Complexes Having an η^<5 : >η^1-(Ind-P)_n Ligand ((Ind-P)_n H=C_9H_7(CH_2)PR_2 ; R=Ph, Cy ; n=2-4)"Organometallics. 17. 4338-4340 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Mashima, T.Abe, and K.Tani: "Asymmetric Transfer Hydrogenation of Ketonic Substrates Catalyzed by (η^5-C_5Me_5)MCl Complexes (M=Rh and Ir) of (1S,2S)-N-(p-Toluenesulfonyl)-1, 2-diphenylethylene-diamine"Chem.Lett.. 1199-1200 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Mashima, T.Abe, and K.Tani: "The Half-sandwich Hydride and 16-Electron Complexes of Rhodium and Iridium Containing (1S, 2S)-N-(p-Toluenesulfonyl)-1,2-diphenylethylenediamine : Relevant to the Asymmetric Transfer Hydrogenation"Chem.Lett.. 1201-1202 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Mashima, Y.Matsuo, and K.Tani: "Polymerization of Methyl Methacrylate Catalyzed by Tantalum-diene Complexes, Ta(η^5-C_5R_5)(η^4-1,3-butadiene)_2 (R=H and Me), in the Presence of Cocatalyst AlMe(OC_6H_2-2,6-(^tBu)_2-4-Me)_2"Proc.Japan Acad.. 74, Ser.B. 217-220 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Kataoka, M.Imanishi, T.Yamagata. and K.Tani: "Direct Observation of Reversible C(sp')-H Bond Activation Characterization of the Structures of Both Ir Complexes before and after C-H Bond Activation by Using a Flexible P-N Heterochelate Hybrid Ligand"Organometallics. 18. 3563-3565 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Tani, A.Iseki and T.Yamagata: "Efficient Transfer Hydrogenation of Alkynes and Alkenes with Methanol Catalysed by Hydrido(methoxo)iridium(III) Complexes"Chem.Commun.. 1821-1822 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Mashima, Y.Matsuo, and K.Tani: "Unique Complexation of 1, 4-Diaza-1, 3-butadiene Ligand on Half-metallocene Fragments of Niobium and Tantalum"Organometallics. 18. 1471-1481 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Kataoka, Y.Iwato, T.Yamagata, and K.Tani: "Third Generation of the Cp'-P Ligand : Highly Stereoselective Control of Central Chirality Arising at a Metal Center"Organometallics. 18. 5423-5425 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Mashima, Y.Matsuo, S.Nakahara, and K.Tani: "1-Aza-1, 3-butadiene Complexes of Tantalum : Preparation and Alkylation of TaCl_2(η^5- C_5 Me_5)(η^4- 1-aza-1, 3-butadiene)"Chem.. 593-594. 69-76 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Kataoka, Y.Iwato, A.Shibahara, T.Yamagata, and K, Tani: "Configurationally Stable Metal-centered Chirality : Stereospecific and Regioselective Rhodaacylation of Alkynes Controlled by the Third Generation of the [Cp'-P]H Ligand"Chem.Commun.. 841-842 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Oshiki, K.Mashima, S-i.Kawamura, K.Tani, and K.Kitaura: "Substituent Effect on Organotin Tp^* Compounds as the Tp^* Reagent for the Preparation of Mono Tp^* Complexes of Group 4-6 Metals (Tp^*= Tris (3, 5-dimethylpyrazol-1-yl)hydroborate)"Bull.Chem.Soc.Jpn.. 73. 1735-1748 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.matsuo, K.Mashima, and K.Tani: "Half-Metallocene Tantalum Complexes Bearing Methyl Methacrylate (MMA) and 1, 4-Diaza-1, 3-diene Ligands as MMA Polymerization Catalysts"Angew.Chem.Int.Ed.. 40(in press). (2001)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2002-03-26  

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