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新規な含高周期典型元素拡張π電子共役系化合物の構築

Research Project

Project/Area Number 18750030
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeSingle-year Grants
Research Field Organic chemistry
Research InstitutionKyoto University

Principal Investigator

笹森 貴裕  Kyoto University, 化学研究所, 助教 (70362390)

Project Period (FY) 2006 – 2007
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2007: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2006: ¥1,900,000 (Direct Cost: ¥1,900,000)
Keywords高周期15族元素 / 立体保護 / ジホスフェン / アントラセン / サイクリックボルタンメトリー / π共役 / 酸化還元 / ビスジホスフェン / フェロセン / 蛍光
Research Abstract

本研究は、新規な含高周期14族および15族元素拡張π電子系の構築とその物性解明を目的としている。本年度は、昨年度合成に成功したアントリルジホスフェンTbtP=PAnth(Tbt=2,4,6-[CH(SiMe_3)_2]_3-C_6H_2,Anth=9-anthry1)のさらなるπ電子拡張を目的とし、アントラセンの9,10位の両方にP=Pユニットを組み込んだ、9,10-ビス(ジボスフェニル)アントラセンの合成を検討した。その結果、初めての安定な9,10-ビス(ジボスフェニル)アントラセンである(ArP=P)C_<14>H_8(P=Par)(1:Ar=Tbt2:Ar=Bbt,Bbt=2,6-[CH(SiMe_3)_2]_2-4-[C(SiMe_3)_3]-C_6H_2)の合成に成功し、その構造・物性を解明した。特にサイクリックボルタンメトリーにより、1および2の酸化還元挙動を解明した。1および2は、それぞれ-1.80Vおよび-1.79V(vs.Ag/Ag^+)に可逆な二電子酸化還元波を示し、さらに還元側に電位を掃引したところ、それぞれ-3.08Vおよび-3.11Vに非可逆および可逆な還元波が観測された。その結果、アントラセンユニットにより架橋されたビスジホスフェンは、興味深い多段階還元特性を有することが判った。また、1および2のX線結晶構造解析の結果、再結晶溶媒によってアントラセン部位に対して二つのジホスフェン部位がsynまたはantiの配向を取る二種類の結晶が得られるという興味深い現象を見出した。今後、新規物性の発現を目的とし、さらに高周期の元素を含むπ電子拡張共役系の構築を検討する。

Report

(2 results)
  • 2007 Annual Research Report
  • 2006 Annual Research Report
  • Research Products

    (46 results)

All 2008 2007 2006

All Journal Article (26 results) (of which Peer Reviewed: 14 results) Presentation (20 results)

  • [Journal Article] Generation, Isolation, and Reactivity of a Kinetically Stabilized Diphosphene Anion Radical2008

    • Author(s)
      N. Nagahora
    • Journal Title

      J. Organomet. Chem. 693

      Pages: 625-632

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Reduction of a Kinetically Stabilized Silabenzene Leading to the Formation of the Corresponding Anion Radical Species2008

    • Author(s)
      T. Matsumoto
    • Journal Title

      Organometallics 27

      Pages: 305-308

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Doubly bonded systems between heavier Group 15 elements2008

    • Author(s)
      T. Sasamori
    • Journal Title

      Dalton Trans. 2008

      Pages: 1395-1408

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Alkali Metal Salts of Borylsilyl Anions Utilizing Highly Crowded Silylboranes and Their Properties2008

    • Author(s)
      T. Kajiwara
    • Journal Title

      Organometallics 27

      Pages: 880-893

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Selenization and Tellurization Reactions of Kinetically Stabilized Dipnictenes2008

    • Author(s)
      T. Sasamori
    • Journal Title

      Phosphorus, Sulfur, and Silican and the Belated Elements 183

      Pages: 998-1002

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Characterization of the First Stable Stannanetellone2008

    • Author(s)
      N. Tokitoh
    • Journal Title

      Phosphorus, Sulfur, and Silicon and the Related Elements 183

      Pages: 948-955

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of a 1-Hydrosilene Stable in Solution and Its Unique Properties2008

    • Author(s)
      S. Ozaki
    • Journal Title

      Organometallics 27

      Pages: 2163-2165

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Properties of a Rhodium Complex Having a Novel β-Ketophosphenato Ligand, a Heavier Congener of a β-Ketoiminato Ligand2007

    • Author(s)
      T. Sasamori
    • Journal Title

      Organometallics 26

      Pages: 3621-3623

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Properties of a Kinetically Stabilized 9-Silaphenanthrene2007

    • Author(s)
      N. Tokitoh
    • Journal Title

      Organometallics 26

      Pages: 4048-4053

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Dichlorido [1,2-Bis (phenylseleno) benzenelpalladium (II)2007

    • Author(s)
      N. Takeda
    • Journal Title

      Acta Cryst. E 63

      Pages: 2546-2546

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Kinetically Stabilized 1,1'-Bis [(E)-diphosphenyl] ferrocenes; Syntheses, Structures, Properties, and Reactivities2007

    • Author(s)
      N. Nagahora
    • Journal Title

      Bull. Chem. Soc. Jpn. 80

      Pages: 1884-1900

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Chalcogenation Reactions of Overcrowded Doubly Bonded Systems between Heavier Group 15 Elements2007

    • Author(s)
      T. Sasamori
    • Journal Title

      Bull. Chem. Soc. Jpn. 80

      Pages: 2425-2435

    • NAID

      10020276018

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] trans-1,2-Diferrocenyl-1,2-difluoroethene2007

    • Author(s)
      N. Nagahora
    • Journal Title

      Acta Cryst. E 63

      Pages: 2702-2702

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of a Donor Molecule with Metal Coordination Sites toward Multifunctional Complexes2007

    • Author(s)
      K. Katoh
    • Journal Title

      Chem. Lett. 36

      Pages: 1122-1123

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Characterization of Functionalized Ferrocenylsilanes Bearing a Bulky Substituent2007

    • Author(s)
      T.Sasamori
    • Journal Title

      Silicon Chem. 3

      Pages: 199-207

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Coordination Chemistry of a Kinetically Stabilized Germabenzene : Syntheses and Properties of Stable η^6-Germabenzene Complexes Coordinated with Transition Metals2007

    • Author(s)
      N.Tokitoh
    • Journal Title

      Chem.Eur.J. 13

      Pages: 1856-1862

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Unexpected Reaction of an Overcrowded 9,10-Dihydroanthrylchlorosilane Leading to the Formation of a Dibenzo-7-silanorbornadiene Derivative2007

    • Author(s)
      T.Sasamori
    • Journal Title

      Chem.Lett. 36

      Pages: 588-589

    • NAID

      10019935423

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Colorimetric recognition of the length of α,ω-diamines in water2007

    • Author(s)
      K.Tsubaki
    • Journal Title

      Tetrahedron Lett. 48

      Pages: 2135-2138

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Atoms-in-Molecules Analysis of Extended Hypervalent 5c-6e C_2Z_2O Interactions at the 1,8,9-Positions of Anthraquinone and 9-Methoxyanthracene Systems2007

    • Author(s)
      W.Nakanishi
    • Journal Title

      Chem.Eur.J. 13

      Pages: 255-268

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Synthesis, Structures, and Properties of Meso-Phosphorylporphyrins : Self-organization through P-oxo-to-Zinc Coordination2007

    • Author(s)
      Y.Matano
    • Journal Title

      Chem.Eur.J. 13

      Pages: 891-901

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Synthesis and Characterization of Two Isomers of 14п-electron Germaaromatics : Kinetically Stabilized 9-Germaanthracene and 9-Germaphenanthrene2006

    • Author(s)
      T.Sasamori
    • Journal Title

      Organometallics 25

      Pages: 3533-3536

    • Related Report
      2006 Annual Research Report
  • [Journal Article] A Kinetically Stabilized Stannanetellone, a Tin-Tellurium Double-Bond Compound2006

    • Author(s)
      T.Tajima
    • Journal Title

      Organometallics 25

      Pages: 3552-3553

    • Related Report
      2006 Annual Research Report
  • [Journal Article] One-electron Reduction of Kinetically Stabilized Dipnictenes : Synthesis of Dipnictene Anion Radicals2006

    • Author(s)
      T.Sasamori
    • Journal Title

      J.Am.Chem.Soc. 128

      Pages: 12582-12588

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Synthesis and Properties of 9-Anthryldiphosphene2006

    • Author(s)
      T.Sasamori
    • Journal Title

      Chem.Lett. 35

      Pages: 1382-1383

    • NAID

      10020134774

    • Related Report
      2006 Annual Research Report
  • [Journal Article] [2+3] Cycloaddition reaction of a kinetically stabilized distibene with a nitrile oxide leading to the formation of a unique heterocyclic compound2006

    • Author(s)
      T.Sasamori
    • Journal Title

      Chemistry of Heterocyclic Compounds 474

      Pages: 1880-1887

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Bottom-Up Synthesis of Optically Active Oligonaphthalenes : Three Different Pathways for Controlling Axial Chirality2006

    • Author(s)
      K.Tsubaki
    • Journal Title

      J.Organomet.Chem. 692

      Pages: 6579-6587

    • Related Report
      2006 Annual Research Report
  • [Presentation] Chemistry of Low-coordinated Species of Heavier Group 15 Elements2008

    • Author(s)
      笹森 貴裕
    • Organizer
      近畿化学協会ヘテロ原子部会平成19年度第3回懇話会
    • Place of Presentation
      大阪市
    • Year and Date
      2008-02-12
    • Related Report
      2007 Annual Research Report
  • [Presentation] Chemistry of Low-coordinated Species of Heavier Group 15 Elements2007

    • Author(s)
      T. Sasamori
    • Organizer
      2007 Workshop on Organometallic Chemistry
    • Place of Presentation
      Wako, Japan
    • Year and Date
      2007-11-09
    • Related Report
      2007 Annual Research Report
  • [Presentation] Synthesis and Properties of Stable Dibromodisilene, Dihydrodisilene, and 1-Hydrosilene2007

    • Author(s)
      T. Sasamori
    • Organizer
      The 1st Asian Silicon Symposium
    • Place of Presentation
      Zao Town, Japan
    • Year and Date
      2007-11-01
    • Related Report
      2007 Annual Research Report
  • [Presentation] Synthesis and Properties of Rhodium Complexes Having a Novel β-Ketophosphenato Ligand.2007

    • Author(s)
      T. Matsumoto
    • Organizer
      The 8th Internarional Conference on Heteroatom Chemistry (ICHAC-8)
    • Place of Presentation
      California, USA
    • Year and Date
      2007-08-14
    • Related Report
      2007 Annual Research Report
  • [Presentation] Elucidation of the Redox Behavior of Kinetically Stabilized Silaaromatic Compounds2007

    • Author(s)
      T. Matsumoto
    • Organizer
      The 8th Internarional Conference on Heteroatom Chemistry (ICHAC-8)
    • Place of Presentation
      California, USA
    • Year and Date
      2007-08-14
    • Related Report
      2007 Annual Research Report
  • [Presentation] Kinetically Stabilized 1,1'-Bis (diphosphenyl) ferrocenes2007

    • Author(s)
      N. Nagahora
    • Organizer
      The 8th Internarional Conference on Heteroatom Chemistry (ICHAC-8)
    • Place of Presentation
      California, USA
    • Year and Date
      2007-08-14
    • Related Report
      2007 Annual Research Report
  • [Presentation] Generation of a 1-Hydrosilene Bearing a Bulky Substituent and Its Unique [6+6] Dimerization2007

    • Author(s)
      S. Ozaki
    • Organizer
      The 8th Internarional Conference on Heteroatom Chemistry (ICHAC-8)
    • Place of Presentation
      California, USA
    • Year and Date
      2007-08-14
    • Related Report
      2007 Annual Research Report
  • [Presentation] Synthesis and Properties of Unique Low-coordinated Organo-silicon Compounds: Hydrosilene, Dihydrodisilene and Dibromodisilene2007

    • Author(s)
      T. Sasamori
    • Organizer
      The 8th Internarional Conference on Heteroatom Chemistry (ICHAC-8)
    • Place of Presentation
      California, USA
    • Year and Date
      2007-08-14
    • Related Report
      2007 Annual Research Report
  • [Presentation] Synthesis of Anthryldiphosphene Derivatives by Taking Advantage of Steric Protection and Their Properties2007

    • Author(s)
      A. Tsurusaki
    • Organizer
      The 8th Internarional Conference on Heteroatom Chemistry (ICHAC-8)
    • Place of Presentation
      California, USA
    • Year and Date
      2007-08-14
    • Related Report
      2007 Annual Research Report
  • [Presentation] Synthesis of a New Heterocyclic System: a Diselenadisiletane Bearing Ferrocenyl Units2007

    • Author(s)
      A. Yuasa
    • Organizer
      The 8th Internarional Conference on Heteroatom Chemistry (ICHAC-8)
    • Place of Presentation
      California, USA
    • Year and Date
      2007-08-14
    • Related Report
      2007 Annual Research Report
  • [Presentation] Some Unique Reactions of Kinetically Stabilized Metallaaromatic Compounds of Heavier Group 14 Elements2007

    • Author(s)
      N. Tokitoh
    • Organizer
      The 8th Internarional Conference on Heteroatom Chemistry (ICHAC-8)
    • Place of Presentation
      California, USA
    • Year and Date
      2007-08-13
    • Related Report
      2007 Annual Research Report
  • [Presentation] Synthesis and Properties of Stable Platinum Complexes Bearing Overcrowded Primary Phosphine Ligands2007

    • Author(s)
      M. Kawai
    • Organizer
      The 8th Internarional Conference on Heteroatom Chemistry (ICHAC-8)
    • Place of Presentation
      California, USA
    • Year and Date
      2007-08-13
    • Related Report
      2007 Annual Research Report
  • [Presentation] Redox Behavior of Kinetically Stabilized Dipnictenes2007

    • Author(s)
      T. Sasamori
    • Organizer
      The 2nd International Conference on Joint Project of Chemical Synthesis Core Research Institutions
    • Place of Presentation
      Kyoto, Japan
    • Year and Date
      2007-08-07
    • Related Report
      2007 Annual Research Report
  • [Presentation] Ligand Exchange Reactions of a Kinetically Stabilized 1,1'-Bis (diphosphenyl) ferrocene with Group 6 Metals2007

    • Author(s)
      N. Nagahora
    • Organizer
      The 14th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Place of Presentation
      Nara, Japan
    • Year and Date
      2007-08-03
    • Related Report
      2007 Annual Research Report
  • [Presentation] Redox Behavior of Kinetically Stabilized Silaaromatic Compounds2007

    • Author(s)
      T. Matsumoto
    • Organizer
      The 12th International Symposium on Novel Aromatic Compounds (ISNA-12)
    • Place of Presentation
      Awaji, Japan
    • Year and Date
      2007-07-23
    • Related Report
      2007 Annual Research Report
  • [Presentation] Recent Progress in the Chemistry of Multiply Bonded Germanium and Tin Compounds2007

    • Author(s)
      N.Tokitoh
    • Organizer
      The 12th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead (ICCOC-GTL-12)
    • Place of Presentation
      Galway, Ireland
    • Year and Date
      2007-07-13
    • Related Report
      2007 Annual Research Report
  • [Presentation] Synthesis and Properties of the First Stable 2-Stannanaphthalene2007

    • Author(s)
      Y. Mizuhata
    • Organizer
      The 12th International Conference on the Coordination and Organometallic Chemistry of Germaniun, Tin and Lead (ICCOC-GTL-12)
    • Place of Presentation
      Galway, Ireland
    • Year and Date
      2007-07-13
    • Related Report
      2007 Annual Research Report
  • [Presentation] Synthesis and Properties of the First Stable 9-Germaphenanthrene2007

    • Author(s)
      K. Inamura
    • Organizer
      The 12th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead (ICCOC-GTL-12)
    • Place of Presentation
      Galway, Ireland
    • Year and Date
      2007-07-10
    • Related Report
      2007 Annual Research Report
  • [Presentation] Selenization and Tellurization Reactions of Kinetically Stabilized Dipnictenes2007

    • Author(s)
      T. Sasamori
    • Organizer
      The 10th International Conference on the Chemistry of Selenium and Tellurium (ICCST-10)
    • Place of Presentation
      Lodz, Poland
    • Year and Date
      2007-06-23
    • Related Report
      2007 Annual Research Report
  • [Presentation] Structures of 1,8-Bis(selanyl)-,1-Selanyl-,8-Seleninyl-, and 1,8-Bis(seleninyl)-naphthalenes in Solid States2007

    • Author(s)
      S. Hayashi
    • Organizer
      The 10th International Conference on the Chemistry of Selenium and Tellurium (ICCST-10)
    • Place of Presentation
      Lodz, Poland
    • Year and Date
      2007-06-23
    • Related Report
      2007 Annual Research Report

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Published: 2006-04-01   Modified: 2016-04-21  

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