• 제목/요약/키워드: Cyclopentadienyl

검색결과 40건 처리시간 0.023초

Cobalt Oxime Sandwich형 화합물을 합성하기 위하여 Oxime류와 (${\eta}^5$-Cyclopentadienyl)cobalt를 포함하는 착물과의 반응 (Reaction of Cobalt Doubledecker Sandwich Complexes with Oximes for Synthesizing Cobalt Oxime Sandwich Complex)

  • 이원식;이혁;변상인;박영배;이광;엄재국;곽영우;김태정
    • 대한화학회지
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    • 제36권2호
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    • pp.305-310
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    • 1992
  • Cobalt 금속 중심으로 cyclopentadienyl을 ${\pi}$-착물로 결합하고, 또 oxime 화합물을 리간드로 하는 cobalt oxime sandwich형 착물을 합성하기 위하여 본 연구를 수행하였다. Cyclopentadienyl-cobalt 부분을 도입하기 위해, (${\eta}^5$-Cyclopentadienyl)bis(ethylene)cobalt (Jonas 시약), (η5-cyclopentadienyl)di(carbonyl)cobalt, 그리고 bis(${\eta}^5$-cyclopentadienyl)cobalt (cobaltocene)의 착물이 사용되었고, oxime을 각각 여러 가지 조건에서 반응시켰다. 그 중에서 Jonas 시약과 dienemonooxime인 2,4-hexadienealdoxime만이 반응되었으며, 그 생성물은 예상을 벗어난 (${\eta}^5$-cyclopentadienyl)(2,4-hexadienenitrile)cobalt [VII]로 밝혀졌다. 이 화합물의 구조는 NMR, mass spectrometer, IR 원소분석기를 통해 확인되었다.

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Tripledecker 착물, $(CpCo)_2(C_4R_4)$과 Alkyne과의 반응 (The Reaction of the Tripledecker Complexes, 4(CpCo)_2(C_4R_4)$ and Alkynes)

  • 엄재국;이원식;김석봉;차진순;이형수;이동호;김홍석;심상철
    • 대한화학회지
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    • 제37권9호
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    • pp.832-836
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    • 1993
  • 트리플데카 착물류, bis-(${\eta}^5-cyclopentadienyl)-{\mu}-({\eta}^4-1,2,3,4-tetraalkylcyclobutadiene$)dicobalt들은 Jonas 시약과 2-hexyne 또는 3-hexyne을 실온에서 동량으로 반응시킬 때, 50% 이상의 최대 수율이 얻어졌다. 한 종류의 트리플데카 착물인 bis-(${\eta}^5-cyclopentadienyl)-{\mu}-({\eta}^4-1,2,3,4-tetraethyl cyclobutadiene$)dicobalt(13)는 실온에서 3-hexyne과 반응시키면, 착물 (${\eta}^5-cyclopentadienyl)cobaltacyclopentadiene-{\mu}-({\eta}^4-2,4-cobaltacyclopentadiene$)(${\eta}^5-cyclopentadienyl$)cobalt(15)로 이성화되었다. 다른 한 종류의 트리플데카 착물, bis-(${\eta}^5-cyclopentadienyl)-{\mu}-({\eta}^4-1,3-dimethyl-2,4-dipropyl cyclobutadiene$)dicobalt(14)를 2-hexyne과 반응시켰더니 1,3,5-trimethyl-2,4,6-tripropylbenzene 화합물이 생성되었다.

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트리플 데카 착물에서부터 Alkynes의 고리화 반응 (A Cyclization of Alkynes from Tripledecker Sandwichcomplexes)

  • 엄재국;박영배;변상인;이혁;곽영우;김태정
    • 대한화학회지
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    • 제35권4호
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    • pp.410-413
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    • 1991
  • 트리플 데카 착물, bis(${\eta}^5$-cyclopentadienyl)-${\mu}$-(${\eta}^6$-2,3-dialkyl-1,4-dimethyl-1,4-dibora-2,5-cyclohexadiene)dicobalt 1을 합성하고, 이것을 출발물질로 하여 여기에 3-hexyne을 과량으로 반응시켰더니 두 종류의 sandwich 착물인 cyclopentadienyl(${\eta}^6$-2,3-dialkyl-1,4-dimethyl-1,4-dibora-2,5-cyclohexadiene)cobalt 2와 cyclopentadienyl(${\eta}^6$-hexaethyl benzene)cobalt 3가 분리되었다. 착물 3은 실온에서 정제하는 동안 분해하여 3-hexyne의 고리화 반응 생성물인 hexaethyl benzene이 생성되었음을 확인하였다.

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1.4-Dibora-2,5-cyclohexadiene 유도체를 리간드로 갖는 니켈 Double-decker 착물의 합성 (Synthesis of Nickel Double-decker Complexes Containing 1,4-Dibora-2,5-cyclohexadiene Derivatives as Ligand)

  • 엄재국
    • 대한화학회지
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    • 제46권3호
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    • pp.213-218
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    • 2002
  • (${\eta}^5$-Cyclopentadienyl)(${\eta}^6$-1,2,3,4-tetramethyl-1,4-dibora-2,5-cyclohexadiene)Ni(5)는 cyclopentadienyl (carbonyl)-nickel dimer와 1,2,3,4-tetramethyl-1,4-dibora-2-cyclohexene (1)을 반응시켜서 주생성물로 얻었다. Di-allyl nickel과 2,3-diethyl-1,4-dimethyl-1,4-dibora-2-cyclohexene (2)을 -20$^{\circ}C$에서 반응시켜서 bis[${\eta}^6$-2,3-dimethyl-1,4-diethoxy-1,4-dibora-2,5-cyclohexadiene]nickel (6) 착화합물을 15% 수율로 생성하였다. 그리고 야-allyl nickel과 2,3-dimethyl-1,4-diethoxy-1,4-dibora-2-cyclohexene (3)을 역시 -20$^{\circ}C$에서 반응시켜서 22% 수율로 bis[${\eta}^6$-2,3-dimethyl-1,4-diethoxy-1,4-dibora-2,5-cyclohexadiene] nickel (7)을 생성하였다. 이들 double-decker 착화합물들은 불안정하여 분리하기 어려웠으며, NMR, MS, 원소분석 등으로 확인하였다.

Syntheses and Structures of 1,2,3-Substituted Cyclopentadienyl Titanium(IV) Complexes

  • Joe, Dae-June;Lee, Bun-Yeoul;Shin, Dong-Mok
    • Bulletin of the Korean Chemical Society
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    • 제26권2호
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    • pp.233-237
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    • 2005
  • Cyclopentadiene compounds, 2-[CR'R(OMe)]-1,3-Me$_2C_5H_3$ (R, R' = 2,2'-biphenyl, 2) and 2-[CR'R(OSiMe$_3$)]-1,3-Me$_2C_5H_3$ (R, R' = 2,2'-biphenyl, 3; R = ph, R' = ph, 4; R = 2-naphthyl, R' = H, 5) are readily synthesized from 2-bromo-3-methoxy-1,3-dimethylcyclopentene (1). Reaction of the cyclopentadienes with Ti(NMe$_2$)$_4$ in toluene results in clean formation of the cyclopentadienyl tris(dimethylamido)titanium complexes, which are transformed to the trichloride complexes, 2-[CR'R(OMe)]-1,3-Me$_2C_5H_2$}TiCl$_3$ (R, R' = 2,2'-biphenyl, 6) and {2-[CR'R(OSiMe$_3$)]-1,3-Me$_2C_5H_2$}TiCl$_3$ (R, R' = 2,2'-biphenyl, 7; R = ph, R' = ph, 8; R = 2-naphthyl, R' = H, 9). Attempts to form C1-bridged Cp/oxido complexes by elimination of MeCl or Me$_3$SiCl were not successful. X-ray structures of 6, 7 and an intermediate complex {2-[Ph$_2$C(OSiMe$_3$)]-1,3-Me$_2C_5H_2$}TiCl$_2$(NMe$_2$) (10) were determined.

Synthesis of Tetradecker Sandwich Complex with 1,4-Dialkyl-1,4-dibora-2,5-cyclohexadiene

  • Jae Kook Uhm;Walter Siebert
    • Bulletin of the Korean Chemical Society
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    • 제13권5호
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    • pp.528-530
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    • 1992
  • A tetradecker sandwich compiex (7a) was synthesized in low yield by the reaction of a tripledecker, bis(${\eta}^5$-cyclopentadienyl)-${\mu}$-(${\eta}^6$-1,2,3,4-tetramethyl 1,4-dibora-2,5-cyclohexadiene) dinickel (5a) with potassium and Fe$Cl_2$${\cdot}$2THF. The reaction of another tripledecker, bis(${\eta}^5$-cyclopentadienyl)-${\mu}$-(${\eta}^6$-2,3-diethyl-1,4-dimethyl-1,4-dibora-2,5-cyclohex adiene) dicobalt (4a) with potassium and Fe$Cl_2$${\cdot}$2THF at room temperature produced a doubledecker complex (2b) via the decomposition of the dark green crystal.