1991 Fiscal Year Annual Research Report

メタラジカルコゲノレン環化合物とククドリシクランとの反応ー付加体生成と解離反応

Research Project

Project/Area Number	03640464
Research Institution	Sophia University
Principal Investigator	梶谷正次上智大学, 理工学部, 助手 (00053702)
Keywords	メタラジカルコゲノレン / メタラジチオレン / クワドリシクラン / コバルト錯体 / ロジウム錯体 / 1,2ーエチレンジチオラト錯体 / ベンゼンジチオラト錯体 / 光解離反応
Research Abstract	遷移金属とそれに配位したカルコゲン原子2個を含む不飽和五員環であるメタラジカルコゲノレン環は芳香族性を有する興味ある環系である。本環系の特性はホスフィン、ホスファイト、アルキン、ジアゾ化合物、アジド化合物や歪化合物であるクワドリシクラン(Q)と反応して1:1付加体(金属およびーカルコゲン結合への)を生成する点にある。本研究ではメタラジカルコゲノレン環の反応特性を解明すべく、シクロペンタジエニル基を有するジカルコゲノラト金属錯体とQとの付加反応に注目し、1.付加体の生成しやうさとその選択性、2.各種付加体の構造、3.付加体の生成機講、4.付加体の熱および光化学的挙動などの解明を目的にした。本年度、研究対象とした錯体は、1、2ージフェニルエチレンジチオラト型とベンゼンジチオラト型の中心金属がCoおよびRh錯体である。本年度の重要な成果として下記の点が挙げられる。1.Rh錯体の方がCo錯体より付加体を生成しやすくかつ一種類の付加体を選択的に与える。Co錯体はエチレンジチオラト型およびベンゼンジチオラト型ともに数種類の付加体を生成した。2.2種類の付加体([Co(cp)(S_2C_6H_4)(C_7H_4)(C_7H_8)]と[Rh(cp)(S_2C_2Ph_2)(C_7H_8)])の単結晶Xー線構造解析に成功した。Co型付加体はCoーS結合に炭化水素(ノルボルネン型)のエッジ部分がCoにブリッジ部分がSに付加している。Rh型付加体は逆にRhーS結合に炭化水素のエッジ部分がSにブリッジ部分がRhに付加している。3.部分的に重水素化されたクワドリシクラン(dsーQ)を合成し、上記の構造既知の付加体を合成した。重水素が付加体の炭化水素のどの分部に分布しているかを調べることにより、付加体生成の際の最初の付加位置とその後の骨格転移を伴う機構を解明した。4.Coの付加体は過剰のQ中で元の錯体に解離するが、Rhの付加体は解離しない。しかし、ともにQのノルボルナジエンへの異性化能を有する。光化学的にはCo,Rh両付加体ともに光解離する。

Research Products
(12 results)

All Other

All Publications (12 results)

[Publications] M.Kajitani: "Isomerization of Quadricyclane to Norbomadiene Catalyzed by(η^5ーCyclopentadienyl)(substituted1,2ーbenzenedithiolato)cobalt(III)Complexes," J.Mol.Catal.
[Publications] M.Kajitani: "Adduct between Quadricyclane and(η^5ーCyclopentadienyl)(1,2ーbenzeneーdithiolato)cobalt(III):Formation and Structure," J.Organomet.Chem.
[Publications] M.Sakurada: "Reaction of Dithiolene with Diazo Compounds:Cycloaddition and Dissociation of Alkylidene Groups," J.Organomet.Chem.423. 141-161 (1992)
[Publications] M.Sakurada: "Reactions of Cobaltadichalcogenolenes with Diazo Compounds;Reactivities of Sulfur and Selenium in Formation and dissociation of AlkyliderneーAdducts," Phosphorus,Sulfur,and Silicon and The Related Elements.
[Publications] A.Kato: "(η^5ーPentadienylcyclopentadienyl)(1ーphenylmethanimineーN,1ーdithiolato)ーcobalt(III)Having a Novel Metallacycle,1,2,5,3ーCobaltadithiazole,in Reactions of〔Co(cp^*(CO)_2〕with Heterocyclic Compounds Containing S and N," Chem.Lett.,. 243-246 (1992)
[Publications] T.Akiyama: "Photochemical Reduction of(η^5ーCyclopentadienyl)(1,2ーdisubstituted 1,2ーethylene dichalcogenolato)cobalt(III)and(η^5ーCyclopentadienyl)(1,2ーbenzenedithiolato)ーcobalt(III)Complexes in the presence of Triethanolamine," Bull.Chem.Soc.Jpn.,.
[Publications] M.Ohtani: "Direct Observations of the Intermediate Species in the Photodissociation of Bis(Sーbenzylー1,2ーdiphenylー1,2ーethylenedithiolato)nickel by Timeーresolved EPR and UVーVis Absorption Spectroscopy," Inorg.Chem.
[Publications] M.Sakurada: "Reactions of Cobaltadichalcogenolenes with Azides.Additions and Dissociations of Imino Groups," Chem.Express. 6. 759-762 (1991)
[Publications] A.Sugimori: "Reactions of Mesoーionic Compounds with Metal Complexes.Formation of(ηーCyclopentadienyl)(1,2ーdiarylー1,2ーethylenedithiolato)cobalt(III)Complexes in the Thermal and Photochemical Reactions of 2,5ーDiarylー1,3ーdithioliumー4ーolate with[Co(cp)]Species," Chem.Lett.269-272 (1991)
[Publications] M.Tono: "Formation of 2,5ーDiarylー1,3ーdithiolyliumー4ーolate in Thermal Reaction of 4ーArylー1,3,2ーoxathiazolyliumー5ーolate," Tetrahedron Lett.32. 4023-4026 (1991)
[Publications] H.Ushijima: "Syntheses and Electrochemical Behavior of Novel Dmit or Dmio Cobalt(III)Complexes with η^5ーCyclopentadienyl or η^5ーPentamethylcyclopentadienyl Ring," Applied Organomet.Chem.5. 221-228 (1991)
[Publications] H.Ushijima: "Effects of Substituents and Chalcogen Atoms on Reduction Halfーwave Potentials of(Substituted ηーcyclopentadienyl)(1,2ーsubstituted 1,2ーethylenediーchalcogenolato)cobalt(III)Complexes in Acetonitrile Solution." J.Electroanal.Chem.303. 199-209 (1991)

1991 Fiscal Year Annual Research Report

メタラジカルコゲノレン環化合物とククドリシクランとの反応ー付加体生成と解離反応

Principal Investigator

梶谷 正次 上智大学, 理工学部, 助手 (00053702)

Research Products

[Publications] M.Kajitani: "Isomerization of Quadricyclane to Norbomadiene Catalyzed by(η^5ーCyclopentadienyl)(substituted1,2ーbenzenedithiolato)cobalt(III)Complexes," J.Mol.Catal.

[Publications] M.Kajitani: "Adduct between Quadricyclane and(η^5ーCyclopentadienyl)(1,2ーbenzeneーdithiolato)cobalt(III):Formation and Structure," J.Organomet.Chem.

[Publications] M.Sakurada: "Reaction of Dithiolene with Diazo Compounds:Cycloaddition and Dissociation of Alkylidene Groups," J.Organomet.Chem.423. 141-161 (1992)

[Publications] M.Sakurada: "Reactions of Cobaltadichalcogenolenes with Diazo Compounds;Reactivities of Sulfur and Selenium in Formation and dissociation of AlkyliderneーAdducts," Phosphorus,Sulfur,and Silicon and The Related Elements.

[Publications] A.Kato: "(η^5ーPentadienylcyclopentadienyl)(1ーphenylmethanimineーN,1ーdithiolato)ーcobalt(III)Having a Novel Metallacycle,1,2,5,3ーCobaltadithiazole,in Reactions of〔Co(cp^*(CO)_2〕with Heterocyclic Compounds Containing S and N," Chem.Lett.,. 243-246 (1992)

[Publications] T.Akiyama: "Photochemical Reduction of(η^5ーCyclopentadienyl)(1,2ーdisubstituted 1,2ーethylene dichalcogenolato)cobalt(III)and(η^5ーCyclopentadienyl)(1,2ーbenzenedithiolato)ーcobalt(III)Complexes in the presence of Triethanolamine," Bull.Chem.Soc.Jpn.,.

[Publications] M.Ohtani: "Direct Observations of the Intermediate Species in the Photodissociation of Bis(Sーbenzylー1,2ーdiphenylー1,2ーethylenedithiolato)nickel by Timeーresolved EPR and UVーVis Absorption Spectroscopy," Inorg.Chem.

[Publications] M.Sakurada: "Reactions of Cobaltadichalcogenolenes with Azides.Additions and Dissociations of Imino Groups," Chem.Express. 6. 759-762 (1991)

[Publications] M.Tono: "Formation of 2,5ーDiarylー1,3ーdithiolyliumー4ーolate in Thermal Reaction of 4ーArylー1,3,2ーoxathiazolyliumー5ーolate," Tetrahedron Lett.32. 4023-4026 (1991)

[Publications] H.Ushijima: "Syntheses and Electrochemical Behavior of Novel Dmit or Dmio Cobalt(III)Complexes with η^5ーCyclopentadienyl or η^5ーPentamethylcyclopentadienyl Ring," Applied Organomet.Chem.5. 221-228 (1991)

[Publications] H.Ushijima: "Effects of Substituents and Chalcogen Atoms on Reduction Halfーwave Potentials of(Substituted ηーcyclopentadienyl)(1,2ーsubstituted 1,2ーethylenediーchalcogenolato)cobalt(III)Complexes in Acetonitrile Solution." J.Electroanal.Chem.303. 199-209 (1991)

梶谷正次上智大学, 理工学部, 助手 (00053702)