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

• Project/Area Number: 03640464
• Research Category: Grant-in-Aid for General Scientific Research (C)
• Allocation Type: Single-year Grants
• Research Field: 有機化学一般
• Research Institution: Sophia University
• Principal Investigator: 梶谷 正次 上智大学, 理工学部, 講師 (00053702)
• Project Period (FY): 1992 – 1993
• Project Status: Completed (Fiscal Year 1992)
• Budget Amount: ¥2,000,000 (Direct Cost: ¥2,000,000); Fiscal Year 1992: ¥400,000 (Direct Cost: ¥400,000); Fiscal Year 1991: ¥1,600,000 (Direct Cost: ¥1,600,000)
• 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-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 / 1,2ーエチレンジチオラト錯体

Research Abstract

メタラジチオレン環は(1)環の芳香族性および(2)金属および金属-S結合の不飽和性という二つの特性に基ずくユニークな反応性を示す環系である。昨年は、(2)の特性に注目し、メタラジチオレン環がひずみ化合物であるクワドリシクラン(Q)と反応して金属-S結合にQが跨がった形で1:1付加体を生成することを見出し、それらの構造と反応性を検討した。付加体の構造に関しては、[Co(cp)(S_2C_6H_4)]とQとの反応で得られた1:1付加体(4種の異性体生成)の中で最も収率の高い付加体(1)と[Rh(cp)(S_2C_2Ph_2)]とQとの反応で得られた1:1付加体(2)(選択的に1種)の二つの付加体のX-線単結晶構造解析に成功した。その結果、Coの付加体1はQがノルボルネンの形に異性化し、そのブリッジがSにまたエッジがCoに、Rhの付加体2はそのブリッジがRhにまたエッジがSにと、Coの場合とは逆の付加形式をもつことがわかった。本年度は、Co錯体とRh錯体との違いに注目し、比較可能なベンゼンジチオラト型のRh錯体[Rh(cp)(S_2C_6H_4)]とQとの付加体(3)の生成とその構造を検討した。その結果、次の点が明かとなった。1.Rh錯体はエチレンジチオラト型およびベンゼンチオラト型ともにほぼ選択的に1種類の付加体を生成した。一方、Co錯体は4種類の付加体を生成した。2.Rh錯体の付加体3の構造(X-線構造解析による)は付加体2の構造と類似の付加形式をしており、付加体の構造は中心金属の違いに依存する。3.重水素化Qを用いてRhおよびCo錯体の付加体を合成し、そのQ部分の重水素の分布を調べることにより、付加体の生成機構を調べた結果、錯体の中心金属のQへ求核攻撃(Rh錯体:エッジ炭素へ、Co錯体:ブリッジヘッド炭素へ)とその後の骨格転移による機構が明かとなった。4.RhおよびCoの付加体はともに光解離し、元の錯体とノルボルナジエンとを与えた。光解離の機構を検討した結果、RhおよびCoの付加体ともにS-C結合の解裂に誘起された競争的な機構が示唆された。

Research Products

• [Publications] Miharu OHTANI: "Direct Observations of the Intermediate Species in the Photodissociation of Bis(S-benzyl-1,2-diphenyl-1,2-ethylenedithiolato)nickel by Time-resolved EPR and UV-Vis Absorption Spectroscopy" Inorg.Chem,. 31. 3873-3874 (1992)
• [Publications] Masami SAKURADA: "Reaction of CpCo{η^5-(S,S,C)-SC(CN)=C(CN)SC'H_2} with P(OMe)_3;Reversible Ring-Expansion and Contraction" Organometallics,. 11[7]. 2337-2339 (1992)
• [Publications] Akihiro KATO: "Formation of (η^5-Pentadienylcyclopentadienyl)-(1-phenylmethanimine-N,1-dithiolato)cobalt(III) Having a Novel Metallacycle,1,2,5,3-Cobaltadithiazole,in Reactions of [Co(cp^*)(CO)_2] with Heterocyclic Compounds Containing S and N" Chem.Lett,. 243-246 (1992)
• [Publications] Takeo AKIYAMA: "Photochemical Reduction of (η^5-Cyclopentadienyl)(1,2-disubstituted 1,2-ethylene dichalcogenolato)cobalt(III) and (η^5-Cyclopentadienyl)-(1,2-benzenedithiolato)cobalt(III) Complexes in the presence of Triethanolamine" Bull.Chem.Soc.Jpn,. 65. 1047-1051 (1992)
• [Publications] Masami SAKURADA: "Reaction of Dithiolene with Diazo Compounds: Cycloaddition and Dissociation of Alkylidene Groups" J.Organomet.Chem,. 423. 141-161 (1992)
• [Publications] Masami SAKURADA: "Reactions of Cobaltadichalcogenolenes with Diazo Compounds; Reactivities of Sulfur and Selenium in Formation and dissociation of Alkylidene-Adducts" Phosphorus,Sulfur,and Silicon and The Related Elements,. 67. 145-150 (1992)
• [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)