trans,cis-RuHCl(PCy₃)₂(CO)₂ | 55100-76-0

• 英文名称: trans,cis-RuHCl(PCy₃)₂(CO)₂
• CAS: 55100-76-0
• 化学式: C₃₈H₆₇ClO₂P₂Ru
• 分子量: 754.419
• InChiKey: XRGSVAVNOSBEDE-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：

  trans,cis-RuHCl(PCy₃)₂(CO)₂ 、 silver trifluoromethanesulfonate 以 四氢呋喃 为溶剂， 以70%的产率得到
  参考文献：
  名称：

  Reactions of Grubbs Catalysts with Excess Methoxide: Formation of Novel Methoxyhydride Complexes

  摘要：

  On exposure to NaOMe (>= 3 equiv) in CH2Cl2-MeOH at 23 degrees C, the first-generation Grubbs catalyst RuCl2(PCy3)(2)(=CHPh) (1a) is immediately transformed into the six-coordinate methoxyhydride complexes RuH(OMe)(CO)(2)(PCy3)(2) (4a) and RuH(OMe)(CO)(H-2)(PCy3)(2) (5a). Complex 5a can be recycled into 4a under conditions conducive to removal of H-2. The second-generation catalyst RuCl2(IMes)(PCy3)(=CHPh) (lb; IMes = N,N'-bis(mesityl)imidazol-2-ylidene) reacts more slowly, requiring several hours even at 20 equiv of NaOMe, and terminates at five-coordinate RuH(OMe)(CO)(IMes)(PCy3) (3b). Experiments in the presence of added PCy3 reveal that consumption of la, but not lb, proceeds via the four-coordinate intermediate formed by equilibrium loss of phosphine, a function of the lability of the PCy3 ligand at ambient temperatures. The poor accessibility of such an intermediate for lb at 23 degrees C retards salt metathesis and inhibits further reaction of 3b. For the bis(PCy3) analogue 3a, fast transformation into 4a is proposed to involve reversible loss of PCy3, coordination of methanol, sigma-metathesis of methanol at the hydride site to liberate H-2, and beta-elimination/decarbonylation of bound methoxide. Competitive uptake of H-2 by 3a yields six-coordinate 5a (the dihydrogen adduct of 3a). Independent routes to RuH(OMe)(CO)(2)(L)(PCy3) (4a/b; a, L = PCy3; b, L = IMes) were developed: these involved sequential transformation of RuHCl(CO)(L)(PCy3) (2a/b) into the bis-carbonyl adducts RuHCl(CO)(2)(L)(PCy3) (7a/b) under CO, conversion of 7a/b into the more reactive triflates RuH(OTf(CO)(2)(L)(PCy3) (8a/b), and reaction of 8a/b with equimolar NaOMe. Dihydride 6b was also prepared, by reaction of 8b with NaH.

  DOI：

  10.1021/om201288p
• 作为产物：
  描述：

  氯化(双三环己基膦)(一氧化碳)(氢)钌 在 羰基硫 作用下， 以 甲苯 为溶剂， 以60%的产率得到trans,cis-RuHCl(PCy₃)₂(CO)₂
  参考文献：
  名称：

  Synthesis and characterization of some ruthenium phosphoniodithiocarboxylate complexes

  摘要：

  DOI：

  10.1021/ic00135a067

文献信息

• Flat and Efficient H<i>CNN</i>and<i>CNN</i>Pincer Ruthenium Catalysts for Carbonyl Compound Reduction
  作者：Steven Giboulot、Salvatore Baldino、Maurizio Ballico、Rosario Figliolia、Alexander Pöthig、Shuanming Zhang、Daniele Zuccaccia、Walter Baratta

  DOI：10.1021/acs.organomet.8b00919

  日期：2019.3.11

  was isolated from 1 by reaction with NEt3. The monocarbonyl complexes trans-[RuCl2(HCNN)(PPh3)(CO)] (5–7) were synthesized from [RuCl2(dmf)(PPh3)2(CO)] and HCNN ligands, while the diacetate trans-[Ru(OAc)2(HCNN)(PPh3)(CO)] (8) was obtained from [Ru(OAc)2(PPh3)2(CO)]. Carbonylation of cis-[RuCl(CNN)(PPh3)2] with CO afforded the pincer derivatives [RuCl(CNN)(PPh3)(CO)] (9–11). Treatment of 9 with Na[BArf]4

  二齿ħ CNN二羰基钌络合物的反式，顺式-将[RuCl 2（H CNN）（CO）2 ]（1 - 3）和反式，顺式-将[RuCl 2（AMPY）（CO）2 ]（1A）通过制备将[RuCl的反应2（CO）2 ] ñ与1- [6-（4'-甲基苯基）吡啶-2-基]甲胺，苯并[ ħ ]喹啉（HC NN），和2-（氨基甲基）吡啶（AMPY ）配体。可替代地，衍生物1 - 3由水合RuCl 3与HCO 2 H和HC NN的反应得到。钳CNN顺-将[RuCl（CNN）（CO）2 ]（4）从分离1通过与净反应3。的单羰基配合物的反式-将[RuCl 2（H CNN）（PPH 3）（CO）]（5 - 7）从将[RuCl合成2（DMF）（PPH 3）2（CO）]和H CNN配体，而双乙酸酯反式-[Ru（OAc）从[Ru（OAc）2（PPh 3）2（CO）]获得2（HC NN）（PPh 3）（CO）]（8）。的羰基化的顺式-将[RuCl（C
• Olivan, Montserrat; Caulton, Kenneth G., Inorganic Chemistry, 1999, vol. 38, # 3, p. 566 - 570
  作者：Olivan, Montserrat、Caulton, Kenneth G.

  DOI：——

  日期：——
• Dynamic Processes in <i>cis</i> Dihydrogen/Hydride Complexes of Ruthenium
  作者：D. Michael Heinekey、Heather Mellows、Tom Pratum

  DOI：10.1021/ja993952h

  日期：2000.7.1