dicarbonylbis(triphenylphosphine)dihydridoiridium hexafluorophosphate | 19392-91-7

• 英文名称: dicarbonylbis(triphenylphosphine)dihydridoiridium hexafluorophosphate
• CAS: 19392-91-7
• 化学式: C₃₈H₃₂IrO₂P₂*F₆P
• 分子量: 919.803
• InChiKey: BYRBAMBFPIPHDQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  dicarbonylbis(triphenylphosphine)dihydridoiridium hexafluorophosphate 、 一氧化碳 在 1-己烯 作用下， 以 苯 为溶剂， 生成 tricarbonylbis(triphenylphosphine)iridium hexafluorophosphate
  参考文献：
  名称：

  均相催化反应的动力学和机理：第7部分。含铑和铱的PPh 3阳离子络合物催化的1-己烯加氢甲酰化

  摘要：

  [M（COD）（PPh 3）2 ] PF 6（M = Rh，1a ; Ir，1b）类型的阳离子铑和铱配合物是1-己烯加氢甲酰化为其相应醛（庚醛和2醛）的有效预催化剂。 -甲基己醛），在甲苯溶液中，在中等压力（2–5 bar）和温度（Rh为60°C，Ir为100°C）下；加氢甲酰化反应中醛的线性与支化比率（l / b）略有变化（Rh在3.0到3.7之间，Ir接近2）。使用这些阳离子配合物作为催化剂前体已经进行了动力学和机理研究。对于两种配合物，反应均根据速率定律r进行。i  =  K 1 K 2 K 3 k 4 [M] [烯烃] [H 2 ] [CO] /（[CO] 2  +  K 1 [H 2 ] [CO] +  K 1 K 2 K 3 [烯烃] [ H 2 ]）。两种配合物均与CO迅速反应，生成相应的三羰基化合物[M（CO）3（PPh 3）2 ] PF 6，M = Rh，2a；Ir，2b，并用合成气制得[MH

  DOI：

  10.1016/j.molcata.2007.01.045
• 作为产物：
  描述：

  bis(η1-tetrahydrothiophene)dihydridobis(triphenylphosphine)iridium hexafluorophosphate 在 CO 、 H₂ 作用下， 以 氯仿 为溶剂， 生成 dicarbonylbis(triphenylphosphine)dihydridoiridium hexafluorophosphate
  参考文献：
  名称：

  HDS模型系统。2,3-二氢噻吩在铱上噻吩均匀氢化为四氢噻吩的中间体

  摘要：

  Thermolysis of the bis(thiophene) (T) dihydride L(PPh3)2Ir(H)2(eta1-SC4H4)2]PF6 (1) in 1,2-dichloroethane at 80-degrees-C gives the thioallyl complex [(PPh3)2IrH(eta4-SC4H5)]PF6 (2) by a stereospecific endo migration of one of the coordinated hydrides. Reaction of the thioallyl complex with H-2 under mild conditions yields the bis(tetrahydrothiophene) (THT) dihydride [(PPh3)2Ir(H)2(eta1-SC4H8)2]PF6 (3) plus the pentahydride [{(PPh3)2IrH}2(mu2-H)3]PF6 (4); if the hydrogenation is carried out in the presence of excess T, complex 3 is obtained exclusively. Interaction of 2 with CO at room temperature produces the two novel isomeric derivatives [(PPh3)2Ir(H)(CO)(eta2-C5,S-SC4H5)]PF6 (7) and [(PPh3)2Ir(H)(CO)(eta2-C3,S-SC4H5)]PF6 (8) in a 5:1 ratio, which do not interconvert from -50 to +80-degrees-C; longer reaction times (24 h, 25-degrees-C) or higher temperatures (3 h, 50-degrees-C) result in quantitative conversion of the complex to [(PPh3)2-Ir(CO)3]PF6, with concomitant liberation of 2,5-dihydrothiophene (2,5-DHT) and 2,3-DHT in a 5:1 ratio. Reaction of 2 with 2,5-DHT under H-2 at 80-degrees-C produces the new bis(2,5-DHT) dihydride complex [(PPh3)2Ir(H)2(eta1-2,5-SC4H6)2]PF6 (5), whereas the analogous reaction with 2,3-DHT results in hydrogenation to yield the bis(THT) dihydride derivative 3. Complex 5 and its 2,3-DHT analog [(PPh3)2Ir(H)2(eta1-2,3-SC4H6)2]PF6 (6) may also be prepared by displacement of coordinated acetone in [(PPh3)2Ir(H)2(Me2CO)2]PF6(5) by the appropriate ligand. Complex 5 does not react with H-2 at 80-degrees-C, whereas 6 is readily transformed into 3 under analogous conditions. Interaction of 2 with syngas results in the production of 7 and 8, together with free 2,5-DHT and 2,3-DHT, plus small amounts of [(PPh3)2Ir(H)2(CO)(eta1-SC4H8)]PF6 (10) and [(PPh3)2Ir(H)2(CO)2]PF6(11). These combined results clearly establish that only the 2,3-DHT isomer is an intermediate in the homogeneous hydrogenation of T to THT (via the isolated thioallyl (2) and hydrido-eta2-C,S (8) intermediates) with this Ir system, a result of relevance in connection with the HDS mechanisms. The THT complex 10 crystallizes in monoclinic space group P2(1) (No. 4) with a = 9.563(4) angstrom, b = 23.201(4) angstrom, c = 11.221(2) angstrom, beta = 97.870 (2), Z = 2, and V = 2466.16 A3. The structure of the complex cation consists of a distorted octahedron with mutually cis-hydrides, cis-THT, and CO and trans-PPh3 ligands.

  DOI：

  10.1021/om00014a050