[(η(6).-cymene)RuCl2(p-toluenesulfonylmethylisonitrile)] | 135944-37-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: [(η(6).-cymene)RuCl2(p-toluenesulfonylmethylisonitrile)]
• 英文别名: [(η(6)-cymene)RuCl2(CNTos)]；dichlororuthenium;1-(isocyanomethylsulfonyl)-4-methylbenzene;1-methyl-4-propan-2-ylbenzene
• CAS: 135944-37-5
• 化学式: C₁₉H₂₃Cl₂NO₂RuS
• 分子量: 501.439
• InChiKey: URSJDXMTOANTIE-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.14
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  46.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 、 对甲基苯磺酰甲基异腈 以 正己烷 为溶剂， 以61.1%的产率得到[(η(6).-cymene)RuCl2(p-toluenesulfonylmethylisonitrile)]
  参考文献：
  名称：

  Synthesis and characterisation of [(η6-cymene)Ru(L)X2] compounds: single crystal X-ray structure of [(η6-cymene)Ru(P{OPh}3)Cl2] at 203 K

  摘要：

  Treatment of the chloro bridged dimer {[(eta(6)-cymene)RuCl](2)(mu-Cl)(2)} (1) with the donor molecules P(OPh)(3), P(OMe)(3), PPh3, PMe3, CO, SMe2, (CNBu)-Bu-t and CNTos in hot hexane causes bridge splitting reactions that produce the monomeric compounds [(eta(6)-cymene)Ru(L)Cl-2], (4)-(11), respectively. Use of the chiral isonitrile S(-)-alpha-methylbenzylisonitrile produced the corresponding complex 12. The diiodo analogues, 13-15, were prepared similarly from {[(eta(6)-cymene)RuI](2)(mu-I)(2)} (3) for P(OPh)(3), P(OMe)(3) and PPh3, respectively. Insertion of tin(II) chloride into both metal-chlorine bonds was observed for [(eta(6)-cymene)Ru(P{OMe}(3))Cl-2] (5), while only monosubstitution was observed for [(eta(6)-cymene)Ru(PPh3)Cl-2] (6). Halide abstraction in the presence of a substrate reaction has been used to prepare some selected cationic compounds which contain an asymmetric ligand environment. Reaction of {[(eta(6)-cymene)RuCl](2)(mu-Cl)(2)} with 1,2-bis(diphenylphosphino)-ethane under ionising conditions produced the cation [(eta(6)-cymene)Ru(dppe)Cl]PF6 (20). Selected compounds have been examined by {C-13-H-1} heteronuclear correlation and {H-1-H-1} COSY and NOESY experiments. The structure of [(eta(6)-cymene)Ru(P{OPh}(3))Cl-2](CH2Cl2)-C-. (4) has been determined at -70degreesC. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2004.06.016

文献信息

• Isocyanide arene-ruthenium(II) complexes and activation of alkenylacetylenes: synthesis and characterization of isocyanide carbene- and mixed carbene-ruthenium compounds
  作者：Rainer Dussel、Didier Pilette、Pierre H. Dixneuf、Wolf Peter Fehlhammer

  DOI：10.1021/om00055a055

  日期：1991.9

  [RuCl2(eta-6-arene)]2 complexes 1 (eta-6-MeC6H4(i)Pr), 2 (eta-6-C6H2Me4), and 3 (eta-6-C6Me6) react with isocyanide CNR [R = (t)Bu (a), C6H11 (b), CH2CO2C6H4Me (c), CH2CO2Et (d), (CH2)4Cl (e), and (CH2)2OSiMe3 (f)] to produce a variety of RUCl2(CNR)(eta-6-arene) derivatives 4-6, which give a C = N absorption in the infrared at high wavenumbers between 2165 and 2206 cm-1. (C6Me6)Cl2RuCN(CH2)2OSiMe3 (6f) on reaction with KF in methanol affords the carbene complex (C6Me6)Cl2Ru:CNHCH2CH2O (8). Cyclic voltammetry of complexes 4-6 shows that only with the most electron-releasing arene C6Me6 a reversible oxidation occurs, at 1.06-1.15 V(SCE) for complexes 6a-f and at 0.80 V(SCE) for 8. Complexes 6a, 6e, and 8 activate isopropenylacetylene, via an allenylidene intermediate, and in the presence of methanol give access to alkenylcarbene complexes containing the Ru = C(OMe)CH = CMe2 moiety 7a,e and the mixed carbene complex 9.