tricarbonylbis(triphenylphosphine)iridium hexafluorophosphate | 50520-11-1

• 英文名称: tricarbonylbis(triphenylphosphine)iridium hexafluorophosphate
• 英文别名: [Ir(CO)3(triphenylphosphine)2]PF6
• CAS: 50520-11-1
• 化学式: C₃₉H₃₀IrO₃P₂*F₆P
• 分子量: 945.797
• InChiKey: ONZPSDDKBDOJRZ-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：

  tricarbonylbis(triphenylphosphine)iridium hexafluorophosphate 在 三乙基硼氢化锂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 HIr(PPh3)2(CO)2
  参考文献：
  名称：

  Tam, Wilson, Organometallics, 1982, vol. 1, # 3, p. 525 - 529

  摘要：

  DOI：
• 作为产物：
  描述：

  在 CO 、 hexamethyldisiloxane 作用下， 以 氘代氯仿 为溶剂， 生成 tricarbonylbis(triphenylphosphine)iridium 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

文献信息

• Transition-metal nitrosyl compounds. Part 13. Some reactions of dinitrosylbis(triphenylphosphine)-cobalt, -rhodium, and -iridium cations
  作者：Sumit Bhaduri、Kevin Grundy、Brian F. G. Johnson

  DOI：10.1039/dt9770002085

  日期：——

  [M(NO)(PPh3)3] and [NO]+when L′= PPh3 but [ML′4]+ when L′= a less bulky phosphine. In contrast, [Co(NO)2(PPh3)2][PF6] gives [Co(NO)2L′2][PF6]. A rationale which accounts for this variation in reactivity is offered. The salt [Co(NO)2(PPh3)2][PF6] reacts with Cl–, Br–, or I–(X–) to provide [Co(NO)2(PPh3)X]; [Ir(NO)2(PPh3)2][PF6] reacts with HCl to form [Ir(NO)(PPh3)2Cl2]. Reaction of [Ir(NO)2(PPh3)2][PF6]

  已经制备了二亚硝酰基阳离子[M（NO）2（PPh 3）2 ] +（M = Co，Rh或Ir），并检查了其中的一些反应。甲31的Rh和Ir中的阳离子的P NMR研究表明，膦交换是primarly经由一个关联过程; 还提供了证据表明与Co的交换主要是通过解离机制进行的。[Rh（NO）2（PPh 3）2 ] +或[Ir（NO）2（PPh 3）2 ] +与叔膦（L'）反应生成[M（NO）（PPh3） 3 ]和[NO] +当L'= PPH 3但[ML' 4 ] +当L'=不太笨重膦。相反，[Co（NO） 2（PPh 3） 2 ] [PF 6 ]得到[Co（NO） 2 L' 2 ] [PF 6 ]。提供了解释这种反应性变化的原理。盐[Co（NO） 2（PPh 3） 2 ] [PF 6 ]与Cl –，Br –或I –（X –）反应生成[Co（NO） 2（PPh 3）X]; [Ir（NO）2（PPh 3）2
• The chemistry of carbonyl(phenylethynyl)bis(triphenylphosphine)iridium(I)
  作者：Robert H. Walter、Brian F. G. Johnson

  DOI：10.1039/dt9780000381

  日期：——

  The title complex has been prepared by a slightly modified route via its carbonyl adduct, and the formation of an intermediate species ‘[lr(HC2Ph)(CO)2(PPh3)2]+’ is suggested. The complex [lr(C2Ph)(CO)(PPh3)2] readily under-goes addition reactions in solution with a wide variety of reagents; in some cases attack is observed only at the metal atom [SO2, HgCl2,H2, O2, CF3CO2H, MeCO2H, C2(CO2Me)2, Mel

  已通过其羰基加合物通过略微修饰的路线制备了标题复合物，并建议形成中间物种“ [lr（HC 2 Ph）（CO）2（PPh 3）2 ] +”。配合物[lr（C 2 Ph）（CO）（PPh 3）2 ]易于在溶液中与多种试剂进行加成反应。在某些情况下，仅在金属原子[SO 2，HgCl 2，H 2，O 2，CF 3 CO 2 H，MeCO 2 H，C 2（CO 2 Me）2，Mel或C 2（CN） 4 ]，以及在金属和乙炔键（HCl，HBr，H1，Cl 2，Br 2或I 2）处的其他位置。
• Kinetics and mechanisms of homogeneous catalytic reactions
  作者：Merlin Rosales、Jesús A. Durán、Ángel González、Inés Pacheco、Roberto A. Sánchez-Delgado

  DOI：10.1016/j.molcata.2007.01.045

  日期：2007.6

  Cationic rhodium and iridium complexes of the type [M(COD)(PPh3)2]PF6 (M = Rh, 1a; Ir, 1b) are efficient precatalysts for the hydroformylation of 1-hexene to its corresponding aldehydes (heptanal and 2-methylhexanal), under mild pressures (2–5 bar) and temperatures (60 °C for Rh and 100 °C for Ir) in toluene solution; the linear to branched ratio (l/b) of the aldehydes in the hydroformylation reaction

  [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