2002 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	立体保護 / かさ高い置換基 / 白金 / カルコゲン / 二重結合化合物 / 酸化反応 / ジカルコゲニド錯体 / ホスフィン配位子
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、目的の遷移金属-カルコゲン二重結合錯体を安定化し、合成・単離することを目的とする。さらに、得られた二重結合錯体の性質を明らかにし、その機能の発現を目指している。既に申請者らは、かさ高い置換基である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)基を用いることにより新規な環構造であるPtS_2環およびPtSe_2環を有するジカルコゲニド白金錯体[(BbtMe_2P)_2PtX_2](X=S, Se)(1)を安定な化合物として合成・単離することに成功している。本年度は、まずジカルコゲニド錯体1の1当量のホスフィン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2[(BbtMe_2P)_2Pt=X](X=S, Se)の合成について検討を行った。しかしながら、1と各種ホスフィンとの反応はホスフィンスルフィド[ArMe_2P=S]を与えるのみであり、目的の2の発生には至らなかった。そこで、1の酸化体[(BbtMe_2P)_2Pt(X_2O_2)](X=S, Se)からの脱XO_2による2の発生を目指して、1の酸化反応について検討を行なった。1と1当量のm-クロロ安息香酸またはt-ブチルヒドロペルオキシドとの反応を行なったところ、対応するX_2O錯体3が得られた。3のさらなる酸化反応を試みたところ、X=Sの場合にはS_2O_3錯体が、X=Seの場合にはSeO_3錯体が得られた。従来の研究では、S_2O錯体を酸化すると対応する1,2-ジスルホキシド体が得られる事が知られており、今回の我々の結果はPtS_2O錯体とPtSe_2O錯体が過剰の酸化剤との反応において従来のS_2O錯体と異なる反応性を示すことを明確に示した例として興味深い。

Research Products

(16 results)

All Other

All Publications (16 results)

[Publications] Takahiro Sasamori: "Syntheses, Structures and Properties of Kinetically Stabilized Distibenes and Dibismuthenes, Novel Doubly Bonded Systems between Heavier Group 15 Elements"Bull. Chem. Soc. Jpn.. 75. 661-675 (2002)
[Publications] Norio Nakata: "Synthesis and Properties of the First Stable Germabenzene"J. Am. Chem. Soc. 124. 6914-6920 (2002)
[Publications] Norihiro Tokitoh: "Systematic Studies on Homo-and Heteronuclear Doubly Bonded Compounds of Heavier Group 15 Elements"Phosphorus, Sulfur and Silicon. 177. 1473-1476 (2002)
[Publications] Kazuto Nagata: "Synthesis of Novel Platinum Dichalcogenido-Complexes by Taking Advantage of Bulky Phosphine Ligands"Phosphorus, sulfur and Silicon. 177. 1859-1862 (2002)
[Publications] Shinro Yasui: "Reaction of Trivalent Phosphorus Compounds with Viologens"Phosphorus, Sulfur and Silicon. 177. 2001-2002 (2002)
[Publications] Takahiro Sasamori: "Synthesis and Reaction of the First Stable Phosphabismuthene, a Novel Compound with Phosphorus-Bismuth Double Bond"Phosphorus, Sulfur and Silicon. 177. 2003-2004 (2002)
[Publications] Norio Nakata: "Reactions of 2-Germanaphthalene with Elemental Sulfur and Selenium Synthesis of Novel Cyclic Polychalcogenides Containing a Germanium, Trichalcogenagermolanes"Chem. Lett.. 818-819 (2002)
[Publications] Yasushi Kawai: "Propanone 2-Chloro-4,6-dinitrophenylhydrazone"Acta Crystallographyca E. 58. o1098-o1099 (2002)
[Publications] Nobuhoro Takeda: "Synthesis and Properties of the First 1-Silanaphthalene"Organometallics. 21. 4024-4026 (2002)
[Publications] Norihoro Tokitoh: "Synthesis and Isolation of the First Germacyclopropabenzene : A Study to Elucidate the Intrinsic Factor for the Ring Deformation of Cyclopropabenzene Skeletons"Organometallics. 21. 4309-4311 (2002)
[Publications] Norio Nakata: "η^6-Germabenzene Complexes of Chromium and Molybdenum"Angew. Chem. Int. Ed.. 42. 115-117 (2003)
[Publications] Norio Nakata: "Synthesis and Properties of the First Stable Neutral Germaaromatic Compound, 2-{2,4,6-Tris[bis(trimethylsilyl)methyl]phenyl}-2-germanaphthalene"Organometallics. 22. 481-489 (2003)
[Publications] Kazuto Nagata: "Unusual Oxidation of Dichalcogenido Complexes of Platinum"Chem. Lett.. 32. 170-171 (2003)
[Publications] Tomoyuki Tajima: "The First Examples of Stable Benzenes Fused with Two Three-membered Rings : Synthesis and Structures of the Two Stereoisomers of Bis(silacyclopropa) benzenes"Chem. Lett.. 32. 220-221 (2003)
[Publications] Takahiro Sasamori: "Synthesis and Reactions of New Diphosphenes Bearing Extremely Bulky Substituents"J. Phys. Org. Chem. (印刷中).
[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-Pentathiagermepane"J. Organomet. Chem. (印刷中).

2002 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] Takahiro Sasamori: "Syntheses, Structures and Properties of Kinetically Stabilized Distibenes and Dibismuthenes, Novel Doubly Bonded Systems between Heavier Group 15 Elements"Bull. Chem. Soc. Jpn.. 75. 661-675 (2002)

[Publications] Norio Nakata: "Synthesis and Properties of the First Stable Germabenzene"J. Am. Chem. Soc. 124. 6914-6920 (2002)

[Publications] Norihiro Tokitoh: "Systematic Studies on Homo-and Heteronuclear Doubly Bonded Compounds of Heavier Group 15 Elements"Phosphorus, Sulfur and Silicon. 177. 1473-1476 (2002)

[Publications] Kazuto Nagata: "Synthesis of Novel Platinum Dichalcogenido-Complexes by Taking Advantage of Bulky Phosphine Ligands"Phosphorus, sulfur and Silicon. 177. 1859-1862 (2002)

[Publications] Shinro Yasui: "Reaction of Trivalent Phosphorus Compounds with Viologens"Phosphorus, Sulfur and Silicon. 177. 2001-2002 (2002)

[Publications] Takahiro Sasamori: "Synthesis and Reaction of the First Stable Phosphabismuthene, a Novel Compound with Phosphorus-Bismuth Double Bond"Phosphorus, Sulfur and Silicon. 177. 2003-2004 (2002)

[Publications] Norio Nakata: "Reactions of 2-Germanaphthalene with Elemental Sulfur and Selenium Synthesis of Novel Cyclic Polychalcogenides Containing a Germanium, Trichalcogenagermolanes"Chem. Lett.. 818-819 (2002)

[Publications] Yasushi Kawai: "Propanone 2-Chloro-4,6-dinitrophenylhydrazone"Acta Crystallographyca E. 58. o1098-o1099 (2002)

[Publications] Nobuhoro Takeda: "Synthesis and Properties of the First 1-Silanaphthalene"Organometallics. 21. 4024-4026 (2002)

[Publications] Norihoro Tokitoh: "Synthesis and Isolation of the First Germacyclopropabenzene : A Study to Elucidate the Intrinsic Factor for the Ring Deformation of Cyclopropabenzene Skeletons"Organometallics. 21. 4309-4311 (2002)

[Publications] Norio Nakata: "η^6-Germabenzene Complexes of Chromium and Molybdenum"Angew. Chem. Int. Ed.. 42. 115-117 (2003)

[Publications] Norio Nakata: "Synthesis and Properties of the First Stable Neutral Germaaromatic Compound, 2-{2,4,6-Tris[bis(trimethylsilyl)methyl]phenyl}-2-germanaphthalene"Organometallics. 22. 481-489 (2003)

[Publications] Kazuto Nagata: "Unusual Oxidation of Dichalcogenido Complexes of Platinum"Chem. Lett.. 32. 170-171 (2003)

[Publications] Tomoyuki Tajima: "The First Examples of Stable Benzenes Fused with Two Three-membered Rings : Synthesis and Structures of the Two Stereoisomers of Bis(silacyclopropa) benzenes"Chem. Lett.. 32. 220-221 (2003)

[Publications] Takahiro Sasamori: "Synthesis and Reactions of New Diphosphenes Bearing Extremely Bulky Substituents"J. Phys. Org. Chem. (印刷中).

[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-Pentathiagermepane"J. Organomet. Chem. (印刷中).

時任宣博京都大学, 化学研究所, 教授 (90197864)