[RuCl(p-cymene)(S2CC3H4N2(C6H2Me3)2)]PF6 | 1174750-05-0

• 英文名称: [RuCl(p-cymene)(S2CC3H4N2(C6H2Me3)2)]PF6
• 英文别名: [RuCl(4-isopropyltoluene)(1,3-di(2,4,6-trimethylphenyl)-imidazolinium-2-dithiocarboxylate)]PF6；[RuCl(p-cymene)(1,3-(Mes)2-imidazolinium-2-dithiocarboxylate)]PF6
• CAS: 1174750-05-0
• 化学式: C₃₂H₄₀ClN₂RuS₂*F₆P
• 分子量: 798.302
• InChiKey: UHMLLGAHPADJJM-UHFFFAOYSA-M

反应信息

• 作为反应物：
  描述：

  potassium thioacetate 、 [RuCl(p-cymene)(S2CC3H4N2(C6H2Me3)2)]PF6 以 二氯甲烷 为溶剂， 以329 mg的产率得到
  参考文献：
  名称：

  含硫配体的阳离子钌芳烃配合物的合成、表征和生物活性

  摘要：

  使用简单的一锅法以几乎定量的产率制备了通式为 [Ru(SAc)(S 2 C·NHC)( p -伞花烃)](PF 6 ) ( 5a–e ) 的五种阳离子钌-芳烃配合物，两步实验程序从[RuCl 2 ( p-伞花烃)] 2 、咪唑(in)鎓-2-二硫代羧酸盐(NHC·CS 2 )两性离子、KSAc和KPF 6开始。这些半夹心化合物通过各种分析技术得到了充分的表征，并且通过X射线衍射分析解析了其中两个的分子结构，揭示了硫代乙酸酯配体的氧原子和近端硫之间存在分子内硫族键二硫代羧酸酯单元的原子。 DFT计算表明C=S … O电荷转移量为2.4 kcal mol -1 。 [Ru(SAc)(S 2 C·IMes)( p -伞花烃)](PF 6 ) ( 5a )在室温下在潮湿的DMSO- d 6中的溶解不会引起其硫配体的解离。相反，对伞花烃缓慢释放以提供可通过质谱检测的 12 电子 [Ru(SAc)(S

  DOI：

  10.1007/s00775-024-02052-2
• 作为产物：
  描述：

  1,3-dimesitylimidazolinium-2-dithiocarboxylate 、 六氟磷酸钾 、 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 以 乙醇 为溶剂， 反应 1.0h， 以69%的产率得到[RuCl(p-cymene)(S2CC3H4N2(C6H2Me3)2)]PF6
  参考文献：
  名称：

  带有咪唑（in）鎓-2-二硫代羧酸配体的水溶性双阴离子和阳离子钌-芳烃配合物的合成、表征和生物活性

  摘要：

  设计了一种有效的合成方案，用于从 [RuCl 2 ( p- cymene)] 2二聚体和2 当量的 NHC·CS 2两性离子制备带有咪唑（in）鎓-2-二硫代羧酸盐配体的五种阳离子钌-芳烃配合物. 反应在室温下在二氯甲烷中干净而迅速地进行，以定量产率提供预期的 [RuCl( p-伞花烃)(S 2 C·NHC)]Cl 产物。当 [RuCl 2 ( p -cymene)] 2二聚体仅与1 当量反应时二硫醇甜菜碱在相同的实验条件下，以定量收率获得了一组具有通式[RuCl(对-伞花烃)(S 2 C·NHC)][RuCl 3 (对-伞花烃)]的五种双金属化合物。这些新颖的双阴离子和阳离子钌-芳烃配合物通过各种分析技术得到了充分表征。NMR滴定表明，二硫代羧酸盐配体螯合得到[RuCl( p-伞花烃)(S 2 C·NHC)] +阳离子是定量的和不可逆的。相反，形成 [RuCl 3 ( p -cymene)]

  DOI：

  10.1021/acs.inorgchem.1c02648
• 作为试剂：
  描述：

  4-乙酰氧基苯甲酸 、 1-己炔 在 [RuCl(p-cymene)(S2CC3H4N2(C6H2Me3)2)]PF6 、 sodium carbonate 作用下， 以 水 、 甲苯 为溶剂， 反应 200.0h， 生成 (Z)-1-hexen-2-yl 4-acetoxybenzoate 、 (E)-1-hexen-2-yl 4-acetoxybenzoate 、 hex-1-en-2-yl 4-acetoxybenzoate
  参考文献：
  名称：

  Ruthenium–arene complexes bearing imidazol(in)ium-2-dithiocarboxylate ligands: Evaluation of their catalytic activity in the synthesis of enol esters

  摘要：

  The catalytic activity of four ruthenium imidazol(in)ium-2-dithiocarboxylates was evaluated for the synthesis of vinyl esters through addition of 4-acetoxybenzoic acid to 1-hexyne, and compared to those of the parent ruthenium-N-heterocyclic carbene complexes and [RuCl2(p-cymene)(PPh3)] (a standard catalyst). It turned out that ruthenium imidazol(in)ium-2-dithiocarboxylates were poorly active and selective. Quantitative yields, indeed, were obtained only after extended reaction times. However, the catalytic activity could be improved significantly under microwave heating or conventional heating in a sealed tube at 160 degrees C, driving the reaction to completion in less than 4 h of reaction. (C) 2009 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2009.08.028

文献信息

• Homoleptic ruthenium(ii) complexes bearing imidazol(in)ium-2-dithiocarboxylate ligands: synthesis, characterization, and redox properties
  作者：Valdemiro P. Carvalho、Guillermo Zaragoza、Lionel Delaude

  DOI：10.1039/d4dt01503g

  日期：——

  dimer with representative imidazol(in)ium-2-dithiocarboxylate zwitterions (NHC·CS2) in the presence of KPF6. The homoleptic complexes were fully characterized by various analytical techniques and the molecular structure of one of them was determined by single-crystal X-ray diffraction analysis. As expected, it featured an octahedral RuS6 core surrounded by three imidazol(in)ium rings and their nitrogen

  用代表性的咪唑（in）裂解[RuCl 2 ( p -cymene)] 2二聚体后，很容易获得通式为[Ru(S 2 C·NHC) 3 ](PF 6 ) 2的五种阳离子钌( II )螯合物。 )2-二硫代羧酸鎓两性离子 (NHC·CS 2 ) 在 KPF 6存在下。通过各种分析技术对均配配合物进行了充分表征，并通过单晶X射线衍射分析确定了其中一种的分子结构。正如预期的那样，它具有一个八面体 RuS 6核心，周围环绕着三个咪唑(in)鎓环及其氮取代基。 Ru-S 键的坚固性与 κ 2 - S , S '-二硫代羧酸盐单元的螯合效应以及大的 1,3-二芳基咪唑（in）鎓基团赋予的空间保护相结合，最有可能解释了这些物种在溶液中。循环伏安法显示，五种均配配合物具有对应于Ru III /Ru II对的单电子氧化还原过程的特征波，相对于Ag/AgCl， E 1/2值范围在0.97至1.27 V之间。 这种
• Synthesis and Catalytic Evaluation of Ruthenium−Arene Complexes Generated Using Imidazol(in)ium-2-carboxylates and Dithiocarboxylates
  作者：Lionel Delaude、Xavier Sauvage、Albert Demonceau、Johan Wouters

  DOI：10.1021/om9002363

  日期：2009.7.27

  The ability of five imidazol(in)ium-2-carboxylates and dithiocarboxylates bearing cyclohexyl, mesityl, or 2,6-diisopropylphenyl substituents on their nitrogen atoms to act as NHC precursors for in situ catalytic applications was probed in ruthenium-promoted ring-opening metathesis and atom transfer radical polymerizations. Results obtained with 1:2 mixtures of [RuCl2(p-cymene)](2) and NHC center dot CO2 adducts were in line with those reported previously starting from preformed [RuCl2-(p-cymene)(NHC)] complexes, whereas the NHC center dot CS2 zwitterions were almost completely inactive. To account for this dichotomy, the preparation of preformed ruthenium-arene complexes from [RuCk(p-cymene)](2) and NHC center dot CX2 inner salts was thoroughly investigated. As expected, imidazolium-2-carboxylates lost their CO2 moiety and afforded [RuCl2(p-cyrnene)(NHC)] complexes in high yields, whereas the NHC center dot CS, betaines retained their zwitterionic nature and led to cationic complexes of the [RuCl(p-cymene)(NHC center dot CS2)]PF6 type. These stable, 18-electron species are the first examples of well-defined transition-metal complexes bearing chelating NHC center dot CS2 ligands. They were characterized by various analytical techniques, and the molecular structure of [RuCl(p-cymene)([Mes center dot CS2)]PF6 was determined by X-ray diffraction analysis.