Ru(Ph)Cl(thiocarbonyl)(triphenylphosphine)2 | 174810-04-9

• 英文名称: Ru(Ph)Cl(thiocarbonyl)(triphenylphosphine)2
• 英文别名: [Ru(C6H5)Cl(CS)(PPh3)2]
• CAS: 174810-04-9
• 化学式: C₄₃H₃₅ClP₂RuS
• 分子量: 782.287
• InChiKey: BNTLWUHMUFHXEG-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  potassium dihydrobis(pyrazol-1-yl)borate 、 Ru(Ph)Cl(thiocarbonyl)(triphenylphosphine)2 以 乙醇 、 二氯甲烷 为溶剂， 以61%的产率得到Ru(Ph)(thiocarbonyl)(triphenylphosphine)2(dihydridobis(pyrazol-1-yl)borate)
  参考文献：
  名称：

  聚唑基螯合物化学。8. 1钌（II）的有机金属二氢双（吡唑-1-基）硼酸盐络合物

  摘要：

  用K [H 2 B（pz）2 ]处理[RuHCl（CO）（PPh 3）3 ]或[RuH（CO）（NCMe）2（PPh 3）2 ] BF 4（pz =吡唑-1- yl）提供[RuH（CO）（PPh 3）2 {H 2 B（pz）2 }]（1），它也是[Ru（SnPh 3）Cl（CO）（PPh 3）反应的产物2 ]或[Ru（SiMe 3）Cl（CO）（PPh 3）2 ]与K [H 2 B（pz）2在乙醇的存在下。[RuHCl（CS）（BTD）（PPh 3）2 ]（BTD = 2,1,3-苯并噻二唑）和[RuHCl（CS）（BSD）（PPh 3）2 ]（BSD = 2,1,3 -苯并硒二唑）是由[RuHCl（CS）（PPh 3）3 ]与BTD或BSD反应制得的。[期RuH（CS）（PPH 3）2 {H 2 B（PZ）2 }]（2）以类似于对的方式获得1从任一[RuHCl（CS）（PPH 3）3 ]或[RuHCl（

  DOI：

  10.1021/om980374p
• 作为产物：
  描述：

  [RuHCl(CS)(PPh3)3] 、 二苯基汞 以 甲苯 为溶剂， 以80%的产率得到Ru(Ph)Cl(thiocarbonyl)(triphenylphosphine)2
  参考文献：
  名称：

  Cycloadditions of Ruthenium Alkylidyne Complexes with Carbonyl or Thiocarbonyl Compounds

  摘要：

  DOI：

  10.1002/anie.199600951

文献信息

• Synthetic and Computational Studies of Thiocarbonyl/σ-Organyl Coupling Reactions
  作者：Jennifer C. Green、Andrew L. Hector、Anthony F. Hill、Sibo Lin、James D. E. T. Wilton-Ely

  DOI：10.1021/om800637y

  日期：2008.11.10

  The reactions of a range of coordinatively unsaturated sigma-organyl thiocarbony] complexes with 1,4,7-trithiacyclononane ([9]aneS(3)) have been investigated, leading in some but not all cases to migratory insertive coupling of thiocarbonyl and sigma-organyl ligands. Thus, under ambient conditions, the reaction of [RuR-Cl(CS)(PPh3)(2)] (R = C(CO2Me)=CHCO2Me, C(C C-CPh)=CHPh, C6H5) with [9]aneS(3) provides sigma-organyl complexes [RuR(CS)(PPh3)([9]aneS(3))](+). On heating, the species [Ru(C6H5)(CS)(PPh3)[9]aneS(3))](+) converts to the thiobenzoyl complex [Ru(eta(2)-SCPh)(PPh3)([9]aneS(3))](+). Similarly the silyl complex [RuCl(SiMe2OEt)-(CS)(PPh3)(2)] with [9]aneS3 provides [Ru(SiMe2OEt)(CS)(PPh3)([9]aneS(3))](+). However, the styryl and stilbenyl complexes [Ru(CR=CHPh)Cl(CS)(PPh3)(2)] (R = H, Ph) under similar conditions provide dihapto thioacyl derivatives [Ru(eta(2)-SCCR=CHPh)(PPh3)([9]aneS(3)](+). The osmium species [Os(CH=CHC6H4Me-4)Cl(CS)-(BTD)(PPh3)(2)] (BTD = 2,1,3-benzothiadiazole), however, yields only the nonmigrated product [Os(CH=CHC6H4Me-4)(CS)(PPh3)([9]aneS(3))](+). Migratory insertion is not induced by other sulfur donor ligands, e.g., CY3PCS2(Cy = cyclohexyl) and Na[S2CNMe2], which provide the complexes [Ru(CH=CH2)(S2CPCy3)-(CS)(PPh3)(2)](+) and [Ru(CH=CHPh)(S2CNMe2)(CS)(PPh3)(2)], respectively. The reactivity of different ligands (R) toward thiocarbonyl migratory insertion in [Ru(R)(CS)(PPh3)([9]aneS(3)](+) was analyzed through density functional theory. The calculated barriers agree qualitatively with experimental observations. In order to determine the electronic effect of substituents on the migrating ligand, a series of hypothetical systems with phenyl ligands varying only in the para-substituent was considered. A general trend that electron-releasing substituents on the migrating ligand promote reaction was observed. Through symmetry-adapted fragment orbital analysis, this phenomenon is determined to correlate well with the energy of the highest occupied,pi-orbital of the ligand.