IrClH(C6H3-2,6-(OPPr(i)2)2) | 1087244-19-6

• 英文名称: IrClH(C6H3-2,6-(OPPr(i)2)2)
• CAS: 1087244-19-6；754216-77-8
• 化学式: C₁₈H₃₂ClIrO₂P₂
• 分子量: 570.071
• InChiKey: MEZCSIHSQNYSDF-UHFFFAOYSA-M

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：

  IrClH(C6H3-2,6-(OPPr(i)2)2) 、 三环己基膦 以 氘代苯 为溶剂， 生成
  参考文献：
  名称：

  Synthesis, characterization and reactivity of iridium pincer complexes

  摘要：

  Using the pincer-ligated iridium fragment [((POCOP)-P-R)Ir] ((POCOP)-P-R = 2,6-bis(di-tert-butyl-phosphonito) benzene or 2,6-bis(di-iso-propyl-phosphonito)benzene), a range of complexes with widely varying steric and electronic properties, have been synthesized and studied. The complexes include the novel Ir species ((POCOP)-P-tBu)Ir(L) (L= MeCN (2), pyridine (3), 2,4,6-triphenylphosphinine (11)), ((POCOP)-P-iPr)Ir(H)(CI)(L) (L = PPh3 (7), PCy3 (8), 2,4,6-triphenylphosphinine (12)) and ((POCOP)-P-iPr)Ir(L) (L = PPh3 (9), PCy3 (10), 2,4,6-triphenylphosphinine (13)). Complex 4, ((POCOP)-P-tBu)Ir(PPh3), serves as a convenient source of the latent WI), 14 -electron species [(`BuPOCOP)Irl, and is susceptible to ligand exchange chemistry; reactions with MeCN and pyridine afford complexes 2 and 3, respectively. Complexes 11-13 represent rare examples of phosphinine-ligated iridium complexes and are the first examples of any pincer -supported metal complex exhibiting coordination to a phosphinine. The solid-state structure of 11 was determined by single crystal X-ray diffraction studies. (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2017.09.005
• 作为产物：
  描述：

  1,3-bis(diisopropylphosphinito)benzene 、 chlorobis(cyclooctene)-iridium(I) dimer 以 甲苯 为溶剂， 以83%的产率得到IrClH(C6H3-2,6-(OPPr(i)2)2)
  参考文献：
  名称：

  Dehydrogenation of alkanes catalyzed by an iridium phosphinito PCP pincer complex

  摘要：

  The novel phosphinito iridium PCP pincer complex, IrH4{C6H3-2,6-(OPPr2')(2)} can be conveniently synthesized and isolated in 74% overall yield. The complex catalyzes the dehydrogenation of linear alkanes to alkenes at the rate of 13 turnovers min(-1) at 200 degreesC. This catalytic activity is slightly higher than that exhibited by iridium complexes of analogous bis(phosphino) PCP ligands. The bis(phosphinito) complex is resistant to decomposition for periods up to 7 days at temperatures as high as 200 degreesC thus matching the thermal stability of the bis(phosphino) pincer complexes. (C) 2004 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2004.01.033
• 作为试剂：
  描述：

  1-苯基-2-吡咯烷酮 在 IrClH(C6H3-2,6-(OPPr(i)2)2) 、 三(五氟苯基)硼烷 、 氢气 、 四(3,5-二(三氟甲基)苯基)硼酸钠 作用下， 以 甲苯 为溶剂， 120.0 ℃ 、5.07 MPa 条件下， 反应 24.0h， 以29%的产率得到1-苯基吡咯烷
  参考文献：
  名称：

  定义明确的铱钳配合物催化酰胺的脱氧加氢

  摘要：

  已经开发了铱催化的酰胺高度化学选择性氢化成胺的方法。使用带有P（O）C（O）P钳形配体与B（C 6 F 5）3结合的明确定义的铱催化剂，在温和的反应条件下可形成C–O裂解产物。该反应提供了一种以高收率和高选择性从酰胺制备胺的新方法。

  DOI：

  10.1021/acscatal.6b01019

文献信息

• Ligand survey results in identification of PNP pincer complexes of iridium as long-lived and chemoselective catalysts for dehydrogenative borylation of terminal alkynes
  作者：Chun-I Lee、Jessica C. DeMott、Christopher J. Pell、Alyson Christopher、Jia Zhou、Nattamai Bhuvanesh、Oleg V. Ozerov

  DOI：10.1039/c5sc02161h

  日期：——

  Following the report on the successful use of SiNN pincer complexes of iridium as catalysts for dehydrogenative borylation of terminal alkynes (DHBTA) to alkynylboronates, this work examined a wide variety of related pincer ligands in the supporting role in DHBTA. The ligand selection included both new and previously reported ligands and was developed to explore systematic changes to the SiNN framework

  继关于成功使用铱的 SiNN 钳形配合物作为末端炔烃 (DHBTA) 脱氢硼化为炔基硼酸盐的催化剂的报告之后，这项工作研究了各种相关钳形配体在 DHBTA 中的支持作用。配体选择包括新的和以前报道的配体，旨在探索 SiNN 框架（8-（2-二异丙基甲硅烷基苯基）氨基喹啉）的系统变化。令人惊讶的是，只有二芳基氨基/双（膦） PNP 系统显示出任何 DHBTA 反应性。筛选中使用的特定 PNP 配体（带有两个二异丙基膦基侧供体）显示 DHBTA 活性低于 SiNN。然而，利用 PNP 系统提供的配体优化机会，通过磷取代的变化导致发现了一种催化剂，其活性、寿命和范围远远超过了原始 SiNN 原型。在模型 PNP 系统中制备了几种 Ir 配合物，并作为催化循环中的潜在中间体进行了评估。其中，(PNP)Ir 二硼基络合物和硼基亚乙烯基络合物显示出催化能力较差，因此可能不是催化循环的一部分。
• Practical Gas Cylinder-Free Preparations of Important Transition Metal-Based Precatalysts Requiring Gaseous Reagents
  作者：Hongwei Sun、Alexander Ahrens、Steffan K. Kristensen、Laurynas Gausas、Bjarke S. Donslund、Troels Skrydstrup

  DOI：10.1021/acs.oprd.1c00205

  日期：2021.10.15

  corresponding precatalysts are of high relevance in the active research fields of C–H bond activation, dehydrogenation, hydrogenation, and coupling reactions. The selection of complexes shown is meant to serve as examples for the usefulness and broadness of the presented methods, allowing precatalysts requiring gaseous reagents to become available for the research community.

  报道了一种用于合成一系列重要的过渡金属基预催化剂的简单而安全的设置，所有这些都需要低分子量气态试剂来制备。氢气、一氧化碳、乙烯和乙炔均以受控方式从封闭的两室反应器中的相应易于处理的前体中释放出来。因此可以避免使用与处理文献中报道的有毒和/或易燃气体相关的气瓶和复杂的设置/技术。相应的预催化剂在 C-H 键活化、脱氢、加氢和偶联反应等活跃的研究领域具有重要意义。所示复合物的选择旨在作为所提出方法的有用性和广泛性的示例，
• Iridium Pincer Catalysts for Silane Dehydrocoupling: Ligand Effects on Selectivity and Activity
  作者：Neil T. Mucha、Rory Waterman

  DOI：10.1021/acs.organomet.5b00486

  日期：2015.8.10

  Catalytic reactions of bisphosphinite pincer-ligated iridium compounds p-X-R(POCOP)IrHC1 (POCOP) [2,6-(R2PO)(2)C6H3, R = Pr-i, X = H (1); R = Bu-t, X = COOMe (2); = H (3); = NMe2 (4)] with primary and secondary silanes have been performed. Complex 1 is primarily a silane redistribution precatalyst, but dehydro coupling catalysis is observed for sterically demanding silane substrates or with aggressive removal of H-2. The bulkier compounds (2-4) are silane dehydrocoupling precatalysts that also undergo competitive redistribution with less hindered substrates. Products generated from reactions utilizing 2-4 include low molecular weight oligosilanes with varying degrees of redistribution present or disilanes when employing more sterically demanding silane substrates. Selectivity for redistribution versus dehydrocoupling depends on the steric and electronic environment of the metal but can also be affected by reaction conditions.