[Ru(C(C6H4Me-4)=CH(C6H4Me-4))Cl(CS)(PPh3)2] | 1000398-58-2

• 英文名称: [Ru(C(C6H4Me-4)=CH(C6H4Me-4))Cl(CS)(PPh3)2]
• 英文别名: [Ru(C(C6H4Me-4)=CHC6H4Me-4)Cl(CS)(PPh3)2]
• CAS: 1000398-58-2
• 化学式: C₅₃H₄₅ClP₂RuS
• 分子量: 912.477
• InChiKey: DVYFNSVLOWHUAE-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：

  1,4,7-三硫环壬烷 、 [Ru(C(C6H4Me-4)=CH(C6H4Me-4))Cl(CS)(PPh3)2] 以 乙醇 、 二氯甲烷 、 水 为溶剂， 以86%的产率得到[Ru(η2-SCC(C6H4Me-4)=CH(C6H4Me-4))(PPh3)(1,4,7-trithiacyclononane)]Cl
  参考文献：
  名称：

  Synthetic and Computational Studies of Thiocarbonyl/σ-Organyl Coupling Reactions

  摘要：

  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.

  DOI：

  10.1021/om800637y
• 作为产物：
  描述：

  [RuHCl(CS)(PPh3)3] 、 1,1'-(1,2-乙炔二基)二(4-甲基苯) 以 四氢呋喃 为溶剂， 以77%的产率得到[Ru(C(C6H4Me-4)=CH(C6H4Me-4))Cl(CS)(PPh3)2]
  参考文献：
  名称：

  钌（II）的五配位单核和双核硫代羰基-链烯基和硫代酰基配合物的合成和反应

  摘要：

  [RuHCl（CS）（PPh 3）3 ]与R 1 C⋮CR 2（R 1 = R 2 = H，Ph，CO 2 Me; R 1 = H，R 2 = C 6 H 4 Me- 4; R 1 = C⋮CPh，R 2 = Ph）导致五或六坐标（R 1 = R 2 = CO 2 Me）σ-烯基配合物[Ru（CR 1 CHR 2）Cl（CS） （PPH 3）2 ]中，芪衍生物存在也通过将[RuCl的热解形成（κ 2 -O在二苯基乙炔的存在下的2 CH）（CS）（PPh 3）2 ]。这些复合物迅速与一氧化碳反应，以提供二齿硫代酰基配合物的[Ru（η 2 -SCCR 1 CHR 2）氯（CO）（PPH 3）2 ]（R 1 = R 2 = H中，Ph; R 1 = H， R 2＝ Ph； R 1＝ C⋮CPh，R 2＝ Ph）或σ-烯基互变异构体[Ru（CR 1 CHR 2）Cl（CO）（CS）（PPh 3）2

  DOI：

  10.1021/om700518m