2003 Fiscal Year Annual Research Report

含高周期14族元素新規芳香族化学種の創製とその構造・物性・機能に関する研究

Research Project

Project/Area Number	14204064
Research Institution	Kyoto University
Principal Investigator	時任宣博京都大学, 化学研究所, 教授 (90197864)
Co-Investigator(Kenkyū-buntansha)	武田亘弘京都大学, 化学研究所, 助手 (80304731)
Keywords	立体保護 / 芳香族化合物 / 光反応 / 9-シラアントラセン / 9,10-Dewar-9-シラアントラセン / [4+4]二量化 / アレーン錯体 / 6属金属
Research Abstract	本研究では、かさ高い置換基を用いた速度論的安定化の手法を利用することにより、含高周期14族元素芳香族化合物を安定化な化合物として合成し、その構造・物性を解明することで、これらの化合物の芳香族性の系統的な評価を行うことを目的としている。さらに、得られた基礎的な知見をもとに、新規な機能性物質開発へと展開することを目指している。申請者らはこれまでに、独自に開発した立体保護基である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)を用いた速度論的安定化の手法により、世界に先駆けて安定なシラベンゼン、1-シラナフタレン、2-シラナフタレン、9-シラアントラセン、2-ゲルマナフタレンを合成・単離し、これらの化学種が母体芳香族炭化水素の系と同様に芳香族性を持つことを明らかにした。アントラセンは光反応により二量体または9,10-デュワーアントラセンに変換されることが知られている。本年度はTbt基を有する9-シラアントラセン1の光反応および熱反応について検討を行った。1の重ベンゼン溶液に300-500nmの光を照射したところ、9,10-Dewar-9-シラアントラセン2の発生を各種スペクトルにより観測した。2は熱的に不安定であり、-80℃においても徐々に1へと異性化した。一方、1を重ベンゼン溶液中110℃において15日間、または固相中180℃において1時間加熱したところ、1の9,10-位でのhead-to-tail型の[4+4]二量化反応が進行した。さらに、Tbt基を有するシラベンゼンと6族金属錯体[M(CH_3CN)_3(CO)_3](M=Cr,Mo,W)との反応を検討し、シラベンゼン環が6族金属にη^6-型で配位したアレーン錯体を合成することに成功した。

Research Products

(16 results)

All Other

All Publications (16 results)

[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)
[Publications] Takahiro Sasamori: "Synthesis and Reactions of New Diphosphenes Bearing Extremely Bulky Substituents"J.Phys.Org.Chem.. 16. 450-462 (2003)
[Publications] Nobuhiro Takeda: "Synthesis and Properties of the First Stable Silylene-Isocyanide Complexes"Chem.Eur.J.. 9. 3530-3543 (2003)
[Publications] Kazuto Nagata: "Synthesis, Structure, and Properties of the First Disulfur and Diselenium Complexes of Platinum"Bull.Chem.Soc.Jpn.. 76. 1577-1587 (2003)
[Publications] Tomoyuki Tajima: "Syntheses and Structures of Silicon Analogues of Cyclopropabenzenes"J.Organomet.Chem.. 686. 118-126 (2003)
[Publications] Akihiro Shinohara: "Photochemical and Thermal Reactions of a Kinetically Stabilized 9-Silaathracene : The First Spectroscopic Observation of a 9,10-Dewar-9-silaanthracene Isomer"J.Am.Chem.Soc.. 125. 10804-10805 (2003)
[Publications] Takahiro Sasamori: "Reaction of an Overcrowded Distibene with Elemental Sulfur and Crystallographic Analysis of the Sulfurization Products"Chem.Lett.. 33. 104-105 (2004)
[Publications] Nobuhiro Takeda: "A Monomeric, Donor-free Lithium Complex with a New Overcrowded beta-Diketiminato Ligand"Chem.Lett.. 33. 134-135 (2004)
[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)
[Publications] Norihito Tokitoh: "New Progress in the Chemistry of Stable Metallaaromatic Compounds of Heavier Group 14 Elements"Acc.Chem.Res.. 37. 86-94 (2004)
[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)
[Publications] Norihiro Tokitoh: "Synthesis of Aromatic Species Containing a Heavier Group 14 Element by Taking Advantage of Kinetic Stabilization (Award Account)"Bull.Chem.Soc.Jpn.. 77. 429-441 (2004)
[Publications] Norihiro Tokitoh: "Stable 2H-Azasilirene and 2H -Phosphasilirene : Addition Reaction of an Ovecrowded Silylene to a Nitrile and a Phosphaalkyne"Silicon.Chem.. (印刷中).
[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)
[Publications] Nobuhiro Takeda: "Science of Syntheses, Houben-Weyl Methods of Molecular Transformations, Category 1 Organometallics, Vol.5. Compounds of Group 14(Ge,Sn,Pb)"Springer-Verlag. 864 (2003)
[Publications] Norihiro Tokitoh: "Reactive Intermediates Chemistry"John Wiley & Sons, Inc. 1072 (2004)

2003 Fiscal Year Annual Research Report

含高周期14族元素新規芳香族化学種の創製とその構造・物性・機能に関する研究

Principal Investigator

時任 宣博 京都大学, 化学研究所, 教授 (90197864)

Research Products

[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)

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

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

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

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

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

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

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

[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)

[Publications] Norihito Tokitoh: "New Progress in the Chemistry of Stable Metallaaromatic Compounds of Heavier Group 14 Elements"Acc.Chem.Res.. 37. 86-94 (2004)

[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)

[Publications] Norihiro Tokitoh: "Synthesis of Aromatic Species Containing a Heavier Group 14 Element by Taking Advantage of Kinetic Stabilization (Award Account)"Bull.Chem.Soc.Jpn.. 77. 429-441 (2004)

[Publications] Norihiro Tokitoh: "Stable 2H-Azasilirene and 2H -Phosphasilirene : Addition Reaction of an Ovecrowded Silylene to a Nitrile and a Phosphaalkyne"Silicon.Chem.. (印刷中).

[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)

[Publications] Nobuhiro Takeda: "Science of Syntheses, Houben-Weyl Methods of Molecular Transformations, Category 1 Organometallics, Vol.5. Compounds of Group 14(Ge,Sn,Pb)"Springer-Verlag. 864 (2003)

[Publications] Norihiro Tokitoh: "Reactive Intermediates Chemistry"John Wiley & Sons, Inc. 1072 (2004)

時任宣博京都大学, 化学研究所, 教授 (90197864)