2003 Fiscal Year Annual Research Report

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 Institution	Kyoto University
Principal Investigator	武田亘弘京都大学, 化学研究所, 助手 (80304731)
Keywords	速度論的安定化 / 立体保護 / 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、高周期典型元素二重結合化学種の合成に有用であった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利用して、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。本年度は、まず、既にその合成に成功している白金-ジカルコゲニド錯体[PtCh_2(PArMe_2)_2](Ch=S, Se)(1)[Angew.Chem.,Int.Ed.,41,136(2002)]の1当量のホスフィン(R_3P:R=Ph,Bu,Me,NMe_2)を用いた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[Pt=Ch(PArMe_2)_2](Ch=S, Se)(2)の合成について検討を行った。しかしながら、いずれの場合にも目的化合物は生成せず、配位子の脱離により生成したと考えられるホスフィンカルコゲニド(ArMe_2P=Ch:Ar=Tbt,Bbt;Ch=S,Se)およびホスフィン(ArMe_2P:Ar=Tbt,Bbt)が得られるのみであった。そこで、より配位能の強い配位子の開発を目指し、新規なビスホスフィン配位子{Bbt(Me)PCH_2}_2(3)を合成した。そして、ビスホスフィン配位子3と[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}](4)の合成に成功した。来年度はこのジクロロ白金錯体4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。

Research Products

(13 results)

All Other

All Publications (13 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-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] 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: "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)

2003 Fiscal Year Annual Research Report

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

Principal Investigator

武田 亘弘 京都大学, 化学研究所, 助手 (80304731)

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-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] 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: "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)

武田亘弘京都大学, 化学研究所, 助手 (80304731)