carbonylhydridotris(triphenylphosphine)iridium(I) | 33541-67-2

• 英文名称: carbonylhydridotris(triphenylphosphine)iridium(I)
• 英文别名: Ir(H)(CO)(PPh₃)₃；HIr(CO)(TPP)₃
• CAS: 33541-67-2
• 化学式: C₅₅H₄₆IrOP₃
• 分子量: 1008.11
• InChiKey: IOPVMNYABUEALT-UHFFFAOYSA-N

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：

  carbonylhydridotris(triphenylphosphine)iridium(I) 在 d-camphor sulfonic acid 作用下， 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Harding, P. Alexander; Preece, Michael; Robinson, Stephen D., Inorganica Chimica Acta, 1986, vol. 118, p. L31 - L34

  摘要：

  DOI：
• 作为产物：
  描述：

  在 triethylamine 作用下， 以 氘代四氢呋喃 为溶剂， 生成 carbonylhydridotris(triphenylphosphine)iridium(I)
  参考文献：
  名称：

  Synthesis of Iridaboratranes Bearing Phosphine-Tethered Borane: Reversible CO/PR₃ (R = Me, OMe, OEt) Substitution Reactions Induced by a σ-Electron-Acceptor Borane Ligand

  摘要：

  The iridaboratrane [{o-(Ph2P)C6H4}(3)B]IrH(CO) (1-Ir), bearing phosphine-tethered borane, was synthesized via phosphine ligand exchange between the tris(triphenylphosphine) carbonyl hydride IrH(CO)(PPh3)(3) (2-Ir) and the tris(phosphine)borane {o-(Ph2P)C6H4}(3)B (3). 1-Ir was fully characterized on the basis of its H-1, B-11, and P-31 NMR spectra, X-ray diffraction analysis, and elemental analysis. Density functional theory calculations revealed the important properties of the a-acceptor borane ligand that led to its unique electron distribution in 1-Ir. The borane ligand extracts a significant amount of electron density from the iridium center, but the iridium center maintains an electron density similar to that of the boron-free compound 2-Ir by decreasing pi back-donation from Ir to CO and strengthening the donation from the phosphorus atom (or by weakening the d(metal)-sigma*(P-R) interaction). The properties of the borane ligand can promote the reversible CO/PR3 (R = Me, OMe, OEt) substitution reaction.

  DOI：

  10.1021/om300216g
• 作为试剂：
  描述：

  对氰基苯乙酮 、 氰乙酸乙酯 在 carbonylhydridotris(triphenylphosphine)iridium(I) 作用下， 以59%的产率得到ethyl (Z)-3-(4-acetylphenyl)-3-amino-2-cyanoprop-2-enoate
  参考文献：
  名称：

  Iridium Hydride Complex Catalyzed Addition of Nitriles to Carbon−Nitrogen Triple Bonds of Nitriles

  摘要：

  DOI：

  10.1021/ja974106e

文献信息

• A novel bidentate silicon containing ligand: cyclopentadienyldimethylsilane
  作者：Ernest Colomer、Robert J.P. Corriu、Roser Pleixats

  DOI：10.1016/0022-328x(90)85457-a

  日期：1990.1

  The dimethylsilylcyclopentadienide anion undergoes cleavage of the silicon-cyclopentadienyl bond upon attempted complexation with transition metals. Complexes bearing such ligands can be obtained by metallation of the cyclopentadienyl ligand in tricarbonyl(η5-cyclopentadienyl)manganese, ferrocene and ruthenocene, followed by reaction with chlorodimethylsilane. The silicon-hydrogen function can react

  尝试与过渡金属络合后，二甲基甲硅烷基环戊二烯阴离子会发生硅-环戊二烯键的裂解。络合物轴承这样的配体可以通过在三羰基环戊二烯基配位体（η的金属化来获得5 -环戊二烯基）锰，二茂铁和二茂钌，接着用氯二甲基硅烷反应。硅-氢官能团可与羰基钴或羰基（氢化）三（三苯基膦）铱反应，得到杂双金属配合物，其中环戊二烯基二甲基硅烷充当组装配体。
• Reactions of co-ordinated ligands. Part X. Reactions of trifluoroacetonitrile with π-allylic complexes of iridium(I) and with dicarbonyl(cyclopentadienyl)methyliron: the molecular and crystal structure of carbonyl(η-cyclopentadienyl)-1-[(1-iminotrifluoroethyl)imino]trifluoroethyl-Nω-iron
  作者：Martin Bottrill、Richard Goddard、Michael Green、Russell P. Hughes、Malcolm K. Lloyd、Susan H. Taylor、Peter Woodward

  DOI：10.1039/dt9750001150

  日期：——

  Reactions of trifluoroacetonitrile with [Ir(π-2-MeC3H4)(CO)(L)2](L = PPh3 or AsPh3) yield six-membered chelate ring complexes [I[graphic omitted]H(CO)(L)](L = PPh3 or AsPh3). A similar reaction of CF3CN with [Ir(π-C3H5)(CO)(PPh3)2] yields [[graphic omitted]H(CO)(PPh3)] together with [[graphic omitted]H(CO)(PPh3)2]. Reactions of [Ir(π-1-MeC3H4)(CO)(PPh3)2], [IrH(CO)2(PPh3)2], or [IrH(CO)(PPh3)3] with

  用的[Ir（π-2-MEC trifluoroacetonitrile的反应3 ħ 4）（CO）（L）2 ]（L = PPH 3或ASPH 3）得到六元螯合环配合物[I [图形省略] H（CO） （L）]（L = PPh 3或ASPh 3）。CF的类似的反应3 CN与物[Ir（π-C 3 H ^ 5）（CO）（PPH 3）2 ]收率[[图形省略] H（CO）（PPH 3）]与[[图形省略1 H （CO）（PPh 3）2 ]。的物[Ir（π-1-MEC反应3 ħ 4）（CO）（PPH 3）2]，具有CF 3 CN的[IrH（CO）2（PPh 3）2 ]或[IrH（CO）（PPh 3）3 ]产生五元螯合环配合物反式-[[省略图]（CF 3） （CO）（PPh 3）2 ]。一个X从CF的反应获得射线络合物的晶体研究3 CN与[FEME（CO）2（η-C 5 H ^ 5）]示出了它具有五元环结构[F
• Trifluoromethyl, difluorocarbene and tetrafluoroethylene complexes of iridium and the crystal structures of IrI(CH3)(CF3)(CO)(PPh3)2, Ir(CF3)(C2F4)(CO)(PPh3)2 and Ir(CF3)(CF2)(CO)(PPh3)2
  作者：Penelope J. Brothers、Anthony K. Burrell、George R. Clark、Clifton E.F. Rickard、Warren R. Roper

  DOI：10.1016/0022-328x(90)87258-f

  日期：1990.8

  trifluoromethyl iridium(I) complex Ir(CF3)(CO)2(PPh3)2 (1 has been prepared by the reaction of Hg(CF3)2 with IrH(CO)2(PPh3)2, or by thermal decomposition of Ir(COCF3)(CO)2(PPh3)2 (3), which is produced from (CF3CO)2O and a reduced iridium(−I) species. Either the reaction of IrH(CO)(PPh3)3 with Hg(CF3)2 or the reversible thermal decarbonylation of 1 yields the coordinatively unsaturated complex Ir(CF3)(CO)(PPh3)2

  三氟甲基铱（I）络合物Ir（CF 3）（CO）2（PPh 3）2（1）是通过Hg（CF 3）2与IrH（CO）2（PPh 3）2反应或通过Ir（COCF 3）（CO）2（PPh 3）2（3）的热分解，它是由（CF 3 CO）2 O和还原的铱（-I）物种产生的。 （PPh 3）3与Hg（CF 3）2或的可逆热脱羰1个产量的配位不饱和的Ir配合物（CF 3）（CO）（PPH 3）2（2）。衍生品Ir（CF 3）L（CO）（PPh 3）2（L = C 2 F 4（4），L = C 2 H 4（5），L = O 2（6））是用1处理四氟乙烯，或分别与乙烯或氧2的化合物。既1和2进行Cl 2，I 2，HCl，H 2和CH 3 I的氧化加成，得到三氟甲基铱（III）络合物IrCl 2（CF 3）（CO）（PPh 3）2（7），IrI 2（CF 3） （CO）（PPh 3）2（8），IrHCl（CF 3）（CO）（PPh
• Novel Halogen Exchange Reactions between Halosilanes and Rh(I) or Ir(I) Complexes
  作者：Hiroshi Yamashita、Toshi-aki Kobayashi、Teruyuki Hayashi、Masato Tanaka

  DOI：10.1246/cl.1989.471

  日期：1989.3

  Vaska-type complexes such as MCl(CO)L2 (M = Rh or Ir, L = tertiary phosphine) or the Wilkinson complex RhCl(PPh3)3 underwent halogen exchange reactions with halosilanes Me3SiX (X = Br, I) to give MX(CO)L2 or RhX(PPh3)3 respectively with the formation of Me3SiCl. The reaction of RhH(CO)(PPh3)3 with MeSiCl3 also afforded RhCl(CO)(PPh3)2.

  Vaska 型配合物如 MCl(CO)L2（M = Rh 或 Ir，L = 叔膦）或 Wilkinson 配合物 RhCl(PPh3)3 与卤代硅烷 Me3SiX (X = Br, I) 进行卤素交换反应，得到 MX( CO)L2 或 RhX(PPh3)3 分别与 Me3SiCl 的形成。RhH(CO)(PPh3)3 与 MeSiCl3 反应也得到 RhCl(CO)(PPh3)2。
• Reactions between carbonylhydridotris(triphenylphosphine)iridium(I) and difluorophosphine oxide, sulphide, and selenide: identification of ionic intermediates
  作者：E. A. V. Ebsworth、Philip G. Page、David W. H. Rankin

  DOI：10.1039/dt9840002569

  日期：——

  Carbonylhydridotris(triphenylphosphine)iridium(I)(1) reacts with PF2HY (Y = O, S, or Se) at 190 K in CH2Cl2 to give [Ir(CO)H2(PPh3)3][PF2Y](2), identified by n.m.r. spectroscopy. When the solutions were allowed to warm above 220 K, PPh3 was liberated and complexes [Ir(CO)H2(PPh3)2(P′F2Y)] were formed [Y = Se, (3a); S, (3b); or O, (3c)]. Complexes (3a) and (3b) were initially produced in two isomeric

  羰基氢化三（三苯基膦）铱（I）（1）在190 K的CH 2 Cl 2中与PF 2 HY（Y = O，S或Se ）反应生成[Ir（CO）H 2（PPh 3）3 ] [ PF 2 Y]（2），通过核磁共振光谱法鉴定。当溶液升温至220 K以上时，释放出PPh 3并形成配合物[Ir（CO）H 2（PPh 3）2（P'F 2 Y）] [Y = Se，（3a）； [ M +（2）]。S，（3b）；或O，（3c）]。配合物（3a）和（3b）最初以两种异构形式生成，其中PPh 3基团互为顺式或互为反式; 在室温下，顺式异构体缓慢异构化为反式异构体。对于复合物（3c）（Y = O），仅检测到反式异构体。在这些反应中形成了副产物[Ir（CO）H（PPh 3）2（P'F 3）]，并报道了其nmr参数。关于（1）的反应中离子中间体的形成的含义，与通常被认为涉及（1）的PPh 3的初始损失的相关反应的机理进行了简要的考虑。