2003 Fiscal Year Annual Research Report

かさ高い置換基を用いたメタラシクロプロパベンゼン類の創製とその性質の解明

Research Project

Project/Area Number	15655011
Research Institution	Kyoto University
Principal Investigator	時任宣博京都大学, 化学研究所, 教授 (90197864)
Keywords	速度論的安定化 / 立体保護 / メタラシクロプロパベンゼン / カルベン錯体 / 6族金属カルボニル錯体 / ジリチオスタンナン / ゲルマニウム / スズ
Research Abstract	芳香環に縮環した三員環を有するシクロプロパベンゼン類は、その高い歪みに由来する特異な構造や反応性などについて興味が持たれ、これまで盛んに研究されている。既に申請者らは、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(以下Tbt基と略)を活用し、ケイ素およびゲルマニウムのジアニオン種であるジリチオシランおよびジリチオゲルマンの発生に成功した。さらにこれらのジリチオメタランと1,2-ジブロモベンゼンとの反応により、縮環した三員環の頂点にケイ素およびゲルマニウム原子を有するシラシクロプロパベンゼンおよびゲルマシクロプロパベンゼンの合成に初めて成功し、それらの構造について報告している。本研究では、これらの研究をさらに高周期元素のスズの系に展開し、スズ原子を有するスタンナシクロプロパベンゼンの合成・単離を行い、炭素、ケイ素、ゲルマニウムの系と比較・検討を行うことにより、メタラシクロプロパベンゼンの構造や性質について系統的な知見を得ることを目的とする。ゲルマシクロプロパベンゼンTbt(Dip)GeC_6H_4(Dip=2,6-ジイソプロピルフェニル)と遷移金属カルボニル錯体[M(CO)_6](M=Cr, Mo, W)との反応を行ったところ、ゲルマニウム-炭素結合へのカルボニル基の挿入反応が進行し、カルベン錯体が生成することが明らかとなった。また、Tbt基を有するジブロモスタンナンTbt(Dip)SnBr2にリチウムナフタレニドを作用させたところ、ヨウ化メチルによる捕捉実験により、ジリチオスタンナンTbt(Dip)SnLi_2(1)の発生が確認された。しかしながら、1と1,2-ジブロモベンゼンとの反応においては、ケイ素やゲルマニウムの系とは異なり、目的のスタンナシクロプロパベンゼンの生成を確認することはできなかった。

Research Products

(16 results)

All Other

All Publications (16 results)

[Publications] Norio Nagata: "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-Silaanthracene : 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] Norihiro 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 Overcrowded 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, Sri, Pb)"George Thieme Velag. 864 (2003)
[Publications] Nobuhiro Takeda: "Topics in Current Chemistry 231, "Elemental Sulfur and Sulfur-Rich Compounds II""Springer-Verlag. 248 (2003)
[Publications] Norihiro Tokitoh: "Reactive Intermediates Chemistry"John Wiley & Sons, Inc. 1072 (2004)

2003 Fiscal Year Annual Research Report

かさ高い置換基を用いたメタラシクロプロパベンゼン類の創製とその性質の解明

Principal Investigator

時任 宣博 京都大学, 化学研究所, 教授 (90197864)

Research Products

[Publications] Norio Nagata: "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-Silaanthracene : 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] Norihiro 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 Overcrowded 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, Sri, Pb)"George Thieme Velag. 864 (2003)

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