| 193084-78-5

• CAS: 193084-78-5
• 化学式: C₂₁H₃₆ClIrOP₂
• 分子量: 594.137
• InChiKey: NWNFKBUYOBTRAG-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：

  在 一氧化碳 、 potassium tert-butylate 作用下， 以 甲苯 、 正戊烷 为溶剂， -35.0~70.0 ℃ 、101.33 kPa 条件下， 反应 72.0h， 生成
  参考文献：
  名称：

  氢加（钳）IrI（CO）配合物：立体和电子因素的重要性

  摘要：

  (POCOP)Ir-I(CO) [POCOP = kappa(3)-C6H3-2,6-(OPR2)(2) for R = Bu-t, Pr-i] and (PCP)Ir-I(CO) [PCP = kappa(3)-C6H3-2,6-(CH2PR2)(2) for R = Bu-t and Pr-i] complexes can add hydrogen via two distinct pathways. When R = Bu-t, (POCOP)Ir(CO) and (PCP)Ir(CO) complexes only add hydrogen via a proton-catalyzed pathway due to steric effects, yielding trans-dihydride complexes. For R = Pr-i, both systems oxidatively add hydrogen to give cis-dihydride complexes which thermally isomerize to more thermodynamically favorable trans-dihydride species, consistent with previous reports. Proton-catalyzed hydrogen addition pathways are also observed for both Pr-i-substituted (pincer)Ir(CO) complexes. (PCP)Ir(CO) complexes add hydrogen under milder conditions than the analogous POCOP species. Intermediate hydrido-pyridine Ir(III) carbonyl complexes from the proton-catalyzed pathway have been synthesized and characterized. This is the first report of a series of complexes shown to add hydrogen via concerted oxidative addition or a proton-catalyzed pathway to the same iridium center.

  DOI：

  10.1021/acs.organomet.6b00598
• 作为产物：
  描述：

  [1,3-亚苯基二(亚甲基)]二(二异丙基膦) 以 甲苯 为溶剂， 反应 34.0h， 生成
  参考文献：
  名称：

  氢加（钳）IrI（CO）配合物：立体和电子因素的重要性

  摘要：

  (POCOP)Ir-I(CO) [POCOP = kappa(3)-C6H3-2,6-(OPR2)(2) for R = Bu-t, Pr-i] and (PCP)Ir-I(CO) [PCP = kappa(3)-C6H3-2,6-(CH2PR2)(2) for R = Bu-t and Pr-i] complexes can add hydrogen via two distinct pathways. When R = Bu-t, (POCOP)Ir(CO) and (PCP)Ir(CO) complexes only add hydrogen via a proton-catalyzed pathway due to steric effects, yielding trans-dihydride complexes. For R = Pr-i, both systems oxidatively add hydrogen to give cis-dihydride complexes which thermally isomerize to more thermodynamically favorable trans-dihydride species, consistent with previous reports. Proton-catalyzed hydrogen addition pathways are also observed for both Pr-i-substituted (pincer)Ir(CO) complexes. (PCP)Ir(CO) complexes add hydrogen under milder conditions than the analogous POCOP species. Intermediate hydrido-pyridine Ir(III) carbonyl complexes from the proton-catalyzed pathway have been synthesized and characterized. This is the first report of a series of complexes shown to add hydrogen via concerted oxidative addition or a proton-catalyzed pathway to the same iridium center.

  DOI：

  10.1021/acs.organomet.6b00598

文献信息

• Unexpected Isomerization of a <i>cis</i>- into a <i>trans</i><i>-</i>Dihydride Complex. A Neutral Late Transition Metal Complex as a Hydride Donor
  作者：Boris Rybtchinski、Yehoshoa Ben-David、David Milstein

  DOI：10.1021/om970104r

  日期：1997.8.1

  cationic complex [HIr(PPh3)(CO)L]Br (5) was obtained in the reaction of 1 with 1,3-bis[(diisopropylphosphino)methyl]-2-bromobenzene (4). Reaction of 5 with KO-t-Bu leads to the Ir(I) complex Ir(CO)L (6), which adds methyl iodide to form IIr(CO)(CH3)L (7). Addition of H2 to 6 results in formation of cis-(L)Ir(H)2(CO) (8). This reaction is reversible, due to the rigid square-planar geometry of 6. Under

  HIr（PPh 3）3（CO）（1）与1,3-双[（二异丙基膦基）甲基]苯（2）在THF或苯中于60°C反应，得到反式-H 2 Ir（CO）L（3； L = C 6 H 3（CH 2 P（i -Pr 2）2）。在1与1,3-的反应中获得阳离子配合物[HIr（PPh 3）（CO）L] Br（5）双[（二异丙基膦基）甲基] -2-溴苯（4）。5与KO- t反应-Bu导致Ir（I）络合物Ir（CO）L（6），后者添加碘代甲烷形成IIr（CO）（CH 3）L（7）。将H 2添加至6导致形成顺式-（L）Ir（H）2（CO）（8）。由于6的刚性正方形平面几何形状，因此此反应是可逆的。在H 2压力下，8异构化为3，表明顺式转变为反式-二氢异构化，这对于八面体络合物来说是前所未有的。该反式-dihydride六个协调复杂的3展品的氢化物的反应性，其是不寻常的中性的后过渡金属络合物和是由于强烈的相互反式的氢化物的配体的影响。各种亲电试剂（[Ph
• Pincer-Ligated Iridium Complexes with Low-Field Ancillary Ligands: Complexes of (iPrPCP)IrCl2 and Comparison with (iPrPCP)IrHCl
  作者：Ashish Parihar、Thomas J. Emge、Srinivas V. S. Chakravartula、Alan S. Goldman

  DOI：10.1021/acs.organomet.4c00162

  日期：2024.6.10

  Yet despite the prevalence of halides as anionic ligands in transition metal chemistry, there are relatively few examples in which both of these ancillary anionic ligands are halides or even other monodentate low-field anions. We report a study of the fragment (iPrPCP)IrCl2 (iPrPCP = κ3-2,6-C6H3(CH2PiPr2)) and adducts thereof. These species are found to be thermodynamically disfavored relative to the

  钳式连接铱配合物已得到广泛开发，而（钳式）Ir(III) 配合物，特别是五配位配合物，是其化学的核心。除了钳配体本身之外，此类复合物通常还带有两个形式上的阴离子配体。然而，尽管卤化物作为过渡金属化学中的阴离子配体很普遍，但这些辅助阴离子配体都是卤化物甚至其他单齿低场阴离子的例子相对较少。我们报告了片段 ( iPr PCP)IrCl 2 ( iPr PCP = κ 3 -2,6-C < b4> H 3 (CH 2 PPr 2 )) 及其加合物。发现这些物质相对于相应的氢化卤化物来说在热力学上是不利的。例如，DFT计算和实验表明，( iPr PCP)IrCl 2 配合物中的一个 Ir-Cl 键会与 H 2 发生反应，得到 ( < b11> PCP)IrHCl或其加合物。在 HCl 水溶液存在下，( iPr PCP)IrCl 2 添加氯离子，得到阴离子过渡金属配合物的一个不寻常的例子 (( iPr