2003 Fiscal Year Annual Research Report

速度論的安定化に基づく含ヘテロ元素動的錯体の自在合成

Research Project

Project/Area Number	14078213
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 / 白金 / カルコゲン / ホスフィン / ジカルコゲニド錯体 / β-ジケチミナト配位子 / リチウム
Research Abstract	本研究では、かさ高い置換基を有する新規な配位子を開発し、これらの配位子上の立体的効果と電子的効果を巧みに組み合わせることにより、新規な結合様式を有する含ヘテロ元素動的錯体を安定化し、合成・単離することを目的とする。さらに、得られた錯体の性質を解明し、その機能の発現を目指す。申請者らは昨年度までの研究において、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(Tbt)基や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(Bbt)基を有する白金ジカルコゲニド錯体[PtCh_2(PArMe_2)_2](1)(Ar=Tbt,Bbt;Ch=S,Se)を合成することに成功した。さらに、1の脱カルコゲン化反応による白金-カルコゲン二重結合化合物2の合成について検討を行ったが、目的の2は発生せず、ホスフィン配位子の脱離が進行することを明らかにした。そこで、より配位能が高いことが予想される新規な二座ホスフィン配位子{Bbt(Me)PCH_2}_2)を合成し、[PtCl_2(cod)_2](cod=cyclooctadiene)との反応によりジクロロ白金錯体[PtCl_2{[Bbt(Me)PCH_2]_2}])(3)の合成に成功した。今後は3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を目指す。さらに、Tbt基を有するリチウムβ-ジケチミナート[Li{(TbtN)C(Me)CHC(Me)(NAr)}](4)(Ar=Ph,Mes)の合成に成功した。4のX線結晶構造解析により、4が初めてのヘテロ原子の配位による安定化のない,結晶中で単量体のリチウムβ-ジケチミナートであることを明らかにした。今後は4用いた低位配位遷移金属錯体の合成について検討を行う予定である。

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 Shinobara: "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,Sn,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

速度論的安定化に基づく含ヘテロ元素動的錯体の自在合成

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 Shinobara: "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,Sn,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)