• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

10族元素-カルコゲン元素間二重結合化学種の創製とその性質の解明

Research Project

Project/Area Number 15750031
Research Category

Grant-in-Aid for Young Scientists (B)

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

Principal Investigator

武田 亘弘  京都大学, 化学研究所, 助手 (80304731)

Project Period (FY) 2003 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2004: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2003: ¥2,200,000 (Direct Cost: ¥2,200,000)
Keywords立体保護 / 白金-硫黄二重結合 / 白金0価錯体 / 二座ホスフィン配位子 / テトラチオエーテル配位子 / 擬六配位構造 / パラジウム / 速度論的安定化 / 白金 / カルコゲン / 二重結合 / ジカルコゲニド錯体 / 10族元素 / ホスフィン
Research Abstract

本研究では,かさ高い置換基である2,4,6-トリス[ビス(トリメチルシリル)メチル]フェニル基[Tbt基]および2,6-ビス[ビス(トリメチルシリル)メチル]-4-[トリス(トリメチルシリル)メチル]フェニル基[Bbt基]を活用した速度論的安定化の手法を用い,10族元素-カルコゲン元素間二重結合化合物を安定な化合物として合成・単離し,その構造および性質を系統的に解明して,その触媒や機能性材料への応用の基礎を築くことを目的としている。
申請者らは昨年度の研究において,Bbt基を有する新規な二座ホスフィン配位子{Bbt(Me)PCH_2}_2(1)を有するジクロロ白金錯体[PtCl_2(1)](2)の合成に成功した。今年度の研究においては,白金-硫黄二重結合化合物の良い前駆体となると考えられる白金0価錯体[Pt(1)](3)の発生について検討を行った。2のNa,リチウムナフタレニド等を用いた還元反応について検討を行ったが,期待された白金0価錯体3の発生は確認されなかった。今後は[PtEt_2(1)]の脱離反応などによる3の発生について検討を行う。
また,末端にTbt基を有するかさ高いテトラチオエーテル配位子Tbt[S(o-phenylene)]_3STbt(4)を合成し,NaPdCl_4との反応によりジクロロパラジウム錯体[PdCl_2(4)](5)を合成することに成功した。5のX線構造解析により,パラジウムが擬6配位構造を有することが明らかとなった。パラジウム(II)錯体は通常平面4配位構造を有することが知られており,6配位パラジウム(II)錯体の報告例は少なく,この結果は非常に興味深い。今後は,5を用いることにより目的の白金-カルコゲン二重結合化合物の合成とその性質の解明について研究を行う予定である。

Report

(2 results)
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (25 results)

All 2005 2004 Other

All Journal Article (12 results) Publications (13 results)

  • [Journal Article] Systematic Studies on Redox Behavior of Homonuclear Double-bond Compounds of Heavier Group 15 Elements2005

    • Author(s)
      Takahiro Sasamori
    • Journal Title

      Chem.Lett. 34

      Pages: 166-167

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Reactions of a Germacyclopropabenzene with Elemental Chalcogens : Syntheses and Structures of a Series of Stable 2H-Benzo[c][1,2]chalcogenagermetes2005

    • Author(s)
      Takahiro Sasamori
    • Journal Title

      Organometallics 24

      Pages: 612-618

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Reactivities of Germacyclopropabenzene toward Some Transition Metal Carbonyl Complexes2005

    • Author(s)
      Tomoyuki Tajima
    • Journal Title

      Appl.Organometal.Chem. 19

      Pages: 570-577

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Synthesis of a Chelate Ring Compound Containing a Lithium Atom by Taking Advantage of a New Unsymmetrical β-Diketiminate Ligand Bearing Bulky Substituents2004

    • Author(s)
      Nobuhiro Takeda
    • Journal Title

      Phosphorus, Sulfur and Silicon 179

      Pages: 727-728

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Synthesis and Properties of the First Disulfur and Diselenium Complexes of Platinum2004

    • Author(s)
      Norihiro Tokitoh
    • Journal Title

      Phosphorus, Sulfur and Silicon 179

      Pages: 915-927

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Reduction of Bis(bromo(mesityl){2,4,6-tris[bis(trimethylsilyl)methyl]phenyl}silyl)butadiyne with Potassium Graphite : Unexpected Formation of 2-Allenyl-1-Benzosilole2004

    • Author(s)
      Yoshiyuki Mizuhata
    • Journal Title

      Phosphorus, Sulfur and Silicon 179

      Pages: 947-948

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Insertion of an Overcrowded Silylene into Hydro- and Haloboranes : A Novel Synthesis of Silylborane Derivatives and Their Properties2004

    • Author(s)
      Takashi Kajiwara
    • Journal Title

      Organometallics 23

      Pages: 4723-4734

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Unprecedented Insertion Reaction of a Silylene into a B-B Bond and Generation of a Novel Borylsilyl Anion by Boron-Metal Exchange Reaction of the Resultant Diborylsilane2004

    • Author(s)
      Takashi Kajiwara
    • Journal Title

      Chem.Commun.

      Pages: 2218-2219

    • Related Report
      2004 Annual Research Report
  • [Journal Article] A Kinetically Stabilized Ferrocenyl Diphosphene : Synthesis, Structure, Properties, and Redox Behavior2004

    • Author(s)
      Noriyoshi Nagahora
    • Journal Title

      Chem.Eur.J. 10

      Pages: 6146-6151

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Syntheses of Polythioethers Tethered with Bulky Aryl Groups and Their Complexation with Late-Transition Metals

    • Author(s)
      Norihiro Tokitoh
    • Journal Title

      Phosphorus, Sulfur, and Silicon (印刷中)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Synthesis of Kinetically Stabilized 1-Silanaphthalenes and Their Properties

    • Author(s)
      Akihiro Shinohara
    • Journal Title

      Bull.Chem.Soc.Jpn. (印刷中)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Telluradistibirane and Telluradibismirane : A New Type of Three-membered Heterocycles of Heavier Main Group Elements

    • Author(s)
      Takahiro Sasamori
    • Journal Title

      Bull.Chem.Soc.Jpn. (印刷中)

    • Related Report
      2004 Annual Research Report
  • [Publications] Norio Nakata: "Reaction of Stable Germabenzene with Chalcogens : Synthesis and Structure of a Novel Germanium Analog of Pentathiepane, 1,2,3,4,5,6-Pentathiagermaepane"J.Organomet.Chem.. 672. 66-71 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Takahiro Sasamori: "Synthesis and Reactions of New Diphosphenes Bearing Extremely Bulky Substituents"J.Phys.Org.Chem.. 16. 450-462 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Nobuhiro Takeda: "Synthesis and Properties of the First Stable Silylene-Isocyanide Complexes"Chem.Eur.J.. 9. 3530-3543 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Kazuto Nagata: "Synthesis, Structure, and Properties of the First Disulfur and Diselenium Complexes of Platinum"Bull.Chem.Soc.Jpn.. 76. 1577-1587 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Tomoyuki Tajima: "Syntheses and Structures of Silicon Analogues of Cyclopropabenzenes"J.Organomet.Chem.. 686. 118-126 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Akihiro Shinohara: "Photochemical and Thermal Reactions of a Kinetically Stabilized 9-Silaanthracene : The First Spectroscopic Observation of a 9,10-Dewar-9-silaanthracene Isomer"J.Am.Chem.Soc.. 125. 10804-10805 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Takahiro Sasamori: "Reaction of an Overcrowded Distibene with Elemental Sulfur and Crystallographic Analysis of the Sulfurization Products"Chem.Lett.. 33. 104-105 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Nobuhiro Takeda: "A Monomeric, Donor-free Lithium Complex with a New Overcrowded beta-Diketiminato Ligand"Chem.Lett.. 33. 134-135 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Tomoyuki Tajima: "Thermal Reactions of an Overcrowded Germacyclopropabenzene with Group 6 Metal Hexacarbonyl Complexes [M(CO)6](M=Cr,Mo,and W) : a Novel Mode of CO Insertion Leading to the Formation of Cyclic Germoxycarbene Metal Complexes"Chem.Commun.. 402-403 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yoshiyuki Mizuhata: "Generation of 1,6-Disilahexapentaene in the Reduction of an Overcrowded Bis (bromodiaryl) butadiyne Leading to the Unexpected Formation of 2-Allenyl-1-benzosilole"Chem.Lett.. 33. 420-421 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Norihiro Tokitoh: "Stable 2H-Azasilirene and 2H-Phosphasilirene : Addition Reaction of an Overcrowded Silylene to a Nitrile and a Phosphaalkyne"Silicon.Chem.. (印刷中).

    • Related Report
      2003 Annual Research Report
  • [Publications] Nobuhiro Takeda: "Science of Syntheses, Houben-Weyl Methods of Molecular Transformations, category 1 Organometallics, Vol.5.Compounds of Group 14 (Ge,Sn,Pb)"George Thieme Velag. 864 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Nobuhiro Takeda: "Topics in Current Chemistry 231, "Elemental Sulfur and Sulfur-Rich Compounds II""Springer-Verlag. 248 (2003)

    • Related Report
      2003 Annual Research Report

URL: 

Published: 2003-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi