[Ru(C(CCPh)=CHPh)Cl(CS)(PPh3)2] | 1000398-34-4

• 英文名称: [Ru(C(CCPh)=CHPh)Cl(CS)(PPh3)2]
• CAS: 1000398-34-4
• 化学式: C₅₃H₄₁ClP₂RuS
• 分子量: 908.445
• InChiKey: MGONSSLIUJTXDM-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：

  哌嗪荒酸 、 [Ru(C(CCPh)=CHPh)Cl(CS)(PPh3)2] 以 甲醇 、 二氯甲烷 为溶剂， 以68%的产率得到[Ru(C(CCPh)=CHPh)(CS)(PPh3)2(piperazine dithiocarbamate)]Cl
  参考文献：
  名称：

  Multimetallic Arrays: Symmetrical and Unsymmetrical Bi-, Tri-, and Tetrametallic Organometallic Complexes of Ruthenium(II) and Osmium(II)

  摘要：

  The cationic complex [Ru(C(C CPh) CHPh)(S,CNC4HgNH2)(CO)(PPh3)(2)](+) was prepared from the reaction of [Ru(C(C CPh)=CHPh)Cl(CO)(BTD)(PPh3)(2)] (BTD = 2,1,3-benzothiadiazole) with the zwitterionic dithiocarbamate H,NCANCS, and characterized structurally. In situ generation of the metal lad ithiocarbamate [Ru(C(C CPh)=CHPh)(SCNC4H8NCS2)(CO)(PPh3)(2)] followed by treatment with [Ru(C(C CPh)=CHPh)c](CO)(BTD)(PPh3)(2)] yielded the symmetrical bimetallic complex [{Ru(C(C CPh)=CHPh)(CO)(PPh3)(2)}(2)(S2CNC4H8NCS2)]. The same product was also accessible by reaction of KS2CNC4H8NCS2K with [Ru(C(C CPh)=CHPh)C](CO)(BTD)(PPh3)(2)]. This direct method also yielded the symmetrical bimetallic complexes [[Ru(CH=CHR)(CO)(PPh3)(2)](2)(S2CNC4H8NCS2)] (R = Bu-t, CPh,OH, C6H4Me-4, CO2Me, CH2OSiMe2,Bu-t) and a tetrametallic species when R = C5H4FeC5H5. The osmium analogues [{Os(CR1=CHR2)(CO)(PPh3)(2))(2)(S2CNC4H8NCS2)] (R1 = C CPh, R-2 = Ph; R-1 = H, R-2 = C6H4Me-4) were also prepared by this method. The stepwise deprotonation and functionalization of [Ru(C(C CPh)=CHPh)(S2CNC4H8NH2)(CO)(PPh3)(2)](+) with NEt3 and CS, was utilized in the generation of the unsymmetrical complexes [{Ru(C(C=-CPh)=CHPh)(CO)(PPh3)(2)} (S(2)CNC(4)HsNCS,) fRu(CH=CHR)(CO)(PPh3)2)] (R = Bu-t, CPh2,OH, C6H4Me-4, COMe, CH2OSiMe2But, C5H4FeC5H5) and the heterobimetallic variant [[Ru(C(C cPh) =(CHPh)(CO)(PPh3)(2))(S2CNC4HNCS2){Os(CH=CHC6H4Me-4)(CO)(PPh3)(2)}]. The mixed carbonyl-thiocarbonyl complex [IRu(C(C CPh)=CHPh)(CO)(PPh3)(2))(S2CNC4H8NCS2)IRu(C(C CPh)=CHPh)(CS)(PPh3)(2))] was also prepared by the same stepwise procedure. These are the first reported examples of alkenyl species bridged by a dithiocarbamate ligand. The similarly unprecedented linked bis(alkynyl)diruthenium complex [(Ru(C CBut)(CO)(PPh3)(2)}(2)(S2CNC4H8NCS2)] was prepared by heating [{Ru(CH=CHC6H4Me-4)(CO)(PPh3)(2)}(2)(S2CNC4H8NCS2)] with excess HC CBut.The first molecular complex bearing all three group 8 metals, [{Ru(C(C CPh)=CHPh)-(CO)(PPh3)(2)}(2)(S2CNC4H8NCS2){Os(CH=CHFc)(CO)(PPh3)(2))], was achieved through the reaction of [Ru(C(C=-CPh)=CHPh)(S2CNC4H2NH2)(CO)(PPh3)(2)](+) with [s(CH=CHFc)CI(CO)(BTD)(PPh3)(2)] (Fc = C5H4FeC5H5, BTD = 2,1,3-benzothiadiazole). Further trimetallic species [(Ru(C(C CPh)=CHPh)(CO)(PPh3)(2)(S2CNC4H8NCS,))(2)M] (M = Ni, Pd, Pt, Zn) were prepared by the reaction of [Ru(C(C CPh)=CHPh)(S2CNC4H2)(CO)(PPh3)(2)](+) with Ni(OAC)(2),PdCl2(NCMe)(2),PtCl2(NCPh)(2) and Zn(OAC)(2) in the presence of NEt3 and CS2.

  DOI：

  10.1021/om800686f

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.