• Title/Summary/Keyword: $RuCl_2(PPh_3)_3$

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Synthesis and Reactions of Organoruthenium(Ⅲ) Complexes (새로운 3가 유기루테늄 착물의 합성과 반응)

  • Lee Dong-Hwan;Kim Hag-Gu;Seo Dae-Ryong;Kim Byung-Soon
    • Journal of the Korean Chemical Society
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    • v.37 no.1
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    • pp.98-104
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    • 1993
  • The paramagnetic organoruthenium(III) complexes $({\eta}^5-C_5Me_5)RuCl_2(PR_3) (PR_3 = PMe_3,\;PEt_3,\;PiPr_3,\;PCy_3,\;PMe_2Ph,\;PMePh_2,\;PPh_3,\;P(p-C_6H_4CH_3)_3$, DPPE, DPPB, Py) (2a∼2k) were synthesized by the reaction of $[({\eta}^5-C_5Me_5)RuCl_2]_2$ (1) with 1 equivalent of the corresponding phosphines $(PR_3)$. The effective magnetic moment ((${\mu}_{eff} = 1.65∼2.07 B.M.$)) derived from the magnetic susceptibility measurements of the complexes (2a∼2k) were consistent with the presence of a "single" unpaired electron in the molecule. Treatment of dichlororuthenium (III) complex ({\eta}^5-C_5Me_5)RuCl_2(PR_3)$ (2) (i) with KBr in acetone afforded the dibromoruthenium (III) complex $({\eta}^5-C_5Me_5)RuBr_2(PR_3) (PR_3 = PPh_3)$, (ii) with sodium amalgam in diethylether led to the bis(phosphine) derivatives $({eta}^5-C_5Me_5)RuCl(PR_3)_2 (PR_3 = PMe_3,\;PMePh_2)$, and (iii) with carbonmonoxide gave to the carbonyl derivatives $({\eta}^5-C_5Me_5)RuCl(PR_3)(CO) (PR_3 = PMe_3,\;PPh_3)$.

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Synthesis of $Cp^*Ru(CO)Cl_2(Cp^*={\eta}^5-C_5Me_5)$ Complex and Reaction with Phosphines ($Cp^*Ru(CO)Cl_2(Cp^*={\eta}^5-C_5Me_5)$착물의 합성과 포스핀과의 반응)

  • Lee, Dong Hwan;Kim, Sng Il;Jun, Jin Hee;Oh, Yung Hee;Kam, Sang Kyu
    • Journal of the Korean Chemical Society
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    • v.41 no.12
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    • pp.639-644
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    • 1997
  • Novel carbonylruthenium (Ⅲ) complex Cp*Ru(CO)Cl2(2, Cp*=η5-C5Me5) was synthesized by the reaction of [Cp*RuCl2]2(1) with CO in toluene. The effective magnetic moment (Veff=1.81 B.M.) derived from the magnetic susceptibility measurement of the complex (2) was consistent with the presence of one "single" unpaired electron. Dibromocarbonylruthenium (Ⅲ) complex Cp*Ru(CO)Br2(3) was obtained by the reaction of complex (2) with KBr in toluene. Complex (2) was easily reduced by the reaction with phosphine in toluene to give the corresponding Ru (Ⅱ) complex Cp*Ru(CO)(PR3)Cl (4a∼4e, PR3=PMe3, PEt3, PMePh2, PPh3, PCy3).

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Ruthenium Catalyzed Synthesis of N-Substituted Perhydroazepine Derivatives (루테늄 촉매를 이용한 N-치환 과수소아제핀 유도체의 합성)

  • Sim, Sang Cheol;Do, Chil Hun;Lee, Seung Yeop;Jo, Wan Ho;Heo, Geun Tae
    • Journal of the Korean Chemical Society
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    • v.34 no.6
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    • pp.652-657
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    • 1990
  • Primary amines react with 1,6-hexanediol at 180$^{\circ}C$ for 5 h under argon atmosphere in the presence of both $RuCl_3{\cdot}3H_2$O and $PR_3$ to give N-substituted perhydroazepine derivatives in good yields. For aromatic amines such as anilines, $RuCl_3{\cdot}3H_2$O combined with $PPh_3$ showed the highest catalytic activity. On the other hand, in the reaction of aliphatic amines, $RuCl_3{\cdot}3H_2$O combined with $PBu_3$ showed the highest catalytic activity. These differences may be attributed to the difference in the basicity of these amines. Less basic aromatic amines may require less basic phosphines, while more basic aliphatic amines may require more basic phosphines as the ligands.

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Synthesis of $Cp^*Ru(CO)(PR_3)H$ Type Complexes and Photo-Induced H/D Exchange Reaction ($Cp^*Ru(CO)(PR_3)H$형 착물의 합성과 광반응에 의한 H/D 교환반응)

  • Lee, Dong Hwan;Kim, Sng Il;Kim, Jang Il;Oh, Yung Hee;Kam, Sang Kyu
    • Journal of the Korean Chemical Society
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    • v.41 no.12
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    • pp.645-652
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    • 1997
  • Hydride complexes Cp*Ru(CO)(PR3)H (Cp*=η5-C5Me5, PR3=PMe3, PEt3, PMePh2, PPh3, PCy3)(4a-4f) were synthesized by the reaction of the corresponding chloro complex Cp*Ru(CO)(PR3)Cl (3a-3f) with various hydridic reagent (NaBH4, LiAlH4, LiBEt3H) or NaOMe. Irradiation of Cp*Ru(CO)(PCy3)H (5e) in C6D6 solution with UV light caused H/D exchange reaction between coordinated Cp*, PCy3 and/or Ru-H ligand proton and a deuterium of the deuterated aromatic solvent through a series of inter- and intramolecular C-H activation. The proposed mechanism was described.

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Synthesis, Spectroscopic Studies of Binuclear Ruthenium(II) Carbonyl Thiosemicarba-zone Complexes Containing PPh3/AsPh3 as Co-ligands: DNA Binding/Cleavage

  • Sampath, K.;Sathiyaraj, S.;Jayabalakrishnan, C.
    • Bulletin of the Korean Chemical Society
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    • v.34 no.2
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    • pp.367-373
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    • 2013
  • The ruthenium(II) ferrocenyl heterocyclic thiosemicarbazone complexes of the type $[RuCl(CO)(EPh_3)]_2L$ (where E = P/As; L = binucleating monobasic tridendate thiosemicarbazone ligand) have been investigated. Strutural features were determined by analytical and spectral techniques. Binding of these complexes with CT-DNA by absorption spectral study indicates that the ruthenium(II) complexes form adducts with DNA and has intrinsic binding constant in the range of $3.3{\times}10^4-1.2{\times}10^5M^{-1}$. The complexes exhibit a remarkable DNA cleavage activity with CT-DNA in the presence of hydrogen oxide and the cleavage activity depends on dosage.

Ruthenium Complex Catalyzed Reaction of Diols or Triol with Amines (루테늄 착물 촉매를 이용한 디올 및 트리올과 아민과의 반응)

  • Sang Chul Shim;Young Zoo Youn;Jae Wook Lee;Dong Yeob Lee;Jae Goo Shim;Ju Hee Kim;Keun Tae Huh
    • Journal of the Korean Chemical Society
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    • v.37 no.11
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    • pp.967-973
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    • 1993
  • ${\alpha},{\omega}$-Diols such as 1,6-hexanediol and 1,7-heptanediol react with secondary amines in the presence of catalytic amount of ruthenium complex at 180$^{\circ}$C for 24 hrs to give the corresponding diamino compounds in good yields. The yield of diamino compound was affected by the molar ratio of ${\alpha},{\omega}$-diol to secondary amine. The reaction was also affected by the nature of the phosphorus ligands employed. On the other hand, aromatic primary amines react with 1,2,6-hexanetriol in the presence of RuCl_3{\cdot}H_2O-3PPh_3$ at 180$^{\circ}$C for 3 hours under argon atmosphere to give selectively 1-substituted aryl-3-hydroxyperhydroazepines in good yields. Selective synthesis of these products show that two primary hydroxy groups (1,6-positions) oxidize predominantly than secondary hydroxy group (2-position) by ruthenium-phosphorus complex. The yields were decreased according to the order of para-, meta- and ortho-substituent.

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