[Ir(COD)H(PPh3)2] | 31781-78-9

• 英文名称: [Ir(COD)H(PPh3)2]
• 英文别名: IrH(COD)(PPh₃)₂
• CAS: 31781-78-9
• 化学式: C₄₄H₄₃IrP₂
• 分子量: 825.993
• InChiKey: SWAMBZCONDESOX-JXNOXZOESA-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：

  [Ir(COD)H(PPh3)2] 、 足球烯 以 苯 为溶剂， 以82.3%的产率得到(η(2)-C60)IrH(C8H12)(PPh3) * 2 C6H6
  参考文献：
  名称：

  有机金属氢化物在富勒烯化学中作为反应物。富勒烯C 60和C 70与HM（CO）（PPh 3）3（MRh和Ir）和HIr（C 8 H 12）（PPh 3）2的相互作用

  摘要：

  富勒烯C 60和C 70与氢化铑和铱氢化物HM（CO）（PPh 3）3（MRh和Ir）和HIr（COD）（PPh 3）2的相互作用具有很高的区域选择性和立体选择性（经由一个三苯基膦分子的取代），并导致仅形成η 2 -衍生物（η 2 -C ñ）MH（CO）（PPH 3）2，其中ñ = 60或70和（η 2 -C 60铱（C 8 H 12）（PPh 3） 分别。通过IR和NMR光谱确定配合物的配位几何形状。已证明这些络合物中的过渡金属原子与1,2键处的C 60分子和1，，9键处的C 70分子配位。

  DOI：

  10.1016/0022-328x(96)06163-3
• 作为产物：
  描述：

  在 P(C₆H₅)3 作用下， 以 氘代氯仿 为溶剂， 生成 [Ir(COD)H(PPh3)2]
  参考文献：
  名称：

  Fernández, Maria J.; Esteruelas, Miguel A.; Oro, Luis A., Organometallics, 1987, vol. 6, # 8, p. 1751 - 1756

  摘要：

  DOI：

文献信息

• The cyclooctadiene ligand in [IrCl(COD)] 2 is hydrogenated under transfer hydrogenation conditions: A study in the presence of PPh 3 and a strong base in isopropanol
  作者：S.M. Wahidur Rahaman、Jean-Claude Daran、Eric Manoury、Rinaldo Poli

  DOI：10.1016/j.jorganchem.2016.10.009

  日期：2017.2

  interaction of [IrCl(COD)]2 with PPh3 in isopropanol has been investigated for various P/Ir ratios, in the absence or presence of a strong base (KOtBu), at room temperature and at reflux. At room temperature, PPh3 adds to the metal center to yield [IrCl(COD)(PPh3)] and additional PPh3 only undergoes rapid degenerative ligand exchange. Subsequent addition of KOtBu affords [IrH(COD)(PPh3)2] as the main

  在不存在或存在强碱（KO t Bu）的情况下，在室温和回流下，研究了[IrCl（COD）] 2与PPh 3在异丙醇中的相互作用以得到各种P / Ir比。在室温下，PPh 3添加到金属中心产生[IrCl（COD）（PPh 3）]，而其他PPh 3仅经历快速的退化配体交换。随后添加KO t Bu可以得到[IrH（COD）（PPh 3）2 ]作为主要化合物，即使在高P / Ir比的情况下也是如此，尽管极少量的产品具有“ HIr（PPh 3）3核心也生成了。升温至溶剂回流温度会导致系统快速（<1 h）并从系统中以氢化产物的形式定量去除COD（根据定量GC分析，为54.4％的环辛烯加32.2％的环辛烷），最终生成了[IrH 3（PPh 3）3 ]。后者以溶剂依赖比例的fac和mer异构体的混合物形式观察到。其他次要产品，建议其中之一为顺-[IrH 2（O i Pr）（PPh 3）3也产生了通过NMR
• Ir-Catalyzed Regioselective Dihydroboration of Thioalkynes toward <i>Gem</i>-Diboryl Thioethers
  作者：Yong Wang、Yuxuan Li、Lei Wang、Shengtao Ding、Lijuan Song、Xinhao Zhang、Yun-Dong Wu、Jianwei Sun

  DOI：10.1021/jacs.2c10881

  日期：2023.2.1

  delivering the two boryl groups, which is remarkable in view of the many competitive paths including monohydroboration, 1,2-dihydroboration, dehydrodiboration, triboration, tetraboration, etc. Control experiments combined with DFT calculations suggested that this process involves two sequential hydroboration events. The second hydroboration requires a higher energy barrier due to severe steric repulsion in

  虽然1,1-二硼基（宝石-二硼基）化合物是有价值的合成基础材料，但目前相关研究主要集中在α-位没有杂官能团的1,1-二硼基烷烃。具有 α- 杂取代基的宝石-二硼基化合物虽然用途广泛，但可获得性有限，因此很少使用。在此，我们开发了第一个杂炔烃的 α-二氢硼化反应，可有效构建偕二硼基、杂取代和四取代碳中心。这种直接、实用、温和且原子经济的反应是对依赖宝石去质子化的传统多步合成策略的有吸引力的补充-二硼基甲烷的强碱。具体而言，[Ir(cod)(OMe)] 2被发现对硫代炔烃的这一过程特别有效，在递送两个硼基时产生出色的 α-区域选择性，这在包括单氢硼化在内的许多竞争路径中非常显着， 1,2-二硼氢化、脱氢硼化、三硼化、四硼化等。控制实验与 DFT 计算相结合表明该过程涉及两个连续的硼氢化事件。第二次硼氢化需要更高的能垒，因为在产生高度拥挤的 α-硫基宝石-二硼基碳中心时存在严重的空间排斥，这是一种以前几乎不为人知的结构基序。
• Iridium-catalyzed formation of trans-polyphenylacetylene by alkyne polymerization
  作者：Mauro Marigo、Dunja Millos、Nazario Marsich、Erica Farnetti

  DOI：10.1016/s1381-1169(03)00415-1

  日期：2003.10

  The iridium(I) compounds HIr(cod)(PR3)(2) (cod: 1,5-cyclooctadiene; PR3: Ph-3, P(p-MeOC6H4)(3), P(o-MeOC6H4)Ph-2, PCyPh2, PCy2Ph) were employed as catalyst precursors for the polymerization of phenylacetylene. The polyene was formed as the major product with all the catalysts except the PCy2Ph derivative, which promoted preferential formation of oligomers. In all cases the polymerization reactions were highly stereoselective, yielding 100% trans-polyphenylacetylene. From the catalytic mixtures the iridium(III) derivatives fac-HIr(CdropCPh)(2)(PR3)(3) (PR3: PPh3, P(p-MeOC6H4)(3)) were isolated. The results of spectroscopic studies are also reported, which provide information on the evolution of the iridium precursors during the catalytic reaction. (C) 2003 Elsevier B.V. All rights reserved.
• Directing iridium-catalyzed C–C bond formation by selection of the ancillary ligands: Polymerization and cyclotrimerization of alkynes
  作者：Erica Farnetti、Serena Filipuzzi

  DOI：10.1016/j.ica.2009.03.030

  日期：2010.2

  The ability of organoiridium derivatives of catalyzing oligomerization and polymerization of terminal alkynes is markedly influenced by the nature of non-participative ligands coordinated to the metal. The dimeric species [Ir(cod)Cl](2) and [Ir(cod)(OMe)](2) (cod = 1,5-cyclooctadiene) as well as the phosphine complexes HIr(cod)(PR(3))(2) (PR(3) = PPh(3), P(p-MeOC(6)H(4))(3), P(o-MeOC(6)H(4))Ph(2), PCyPh(2)) catalyze the polymerization reaction, whereas the diphosphine derivatives HIr(cod)(P-P) (P-P = Ph(2)P(CH(2)) nPPh(2) (n = 1-4), o-C(6)H(4)(PPh(2))(2)) promote the regioselective formation of 1,2,4-trisubstituted benzenes. On the other hand, the iridium complexes with nitrogen chelating ligands Ir(cod)(N-N) X and Ir(hd)(N-N) X (hd = 1,5-hexadiene; N-N = 1,10-phenanthroline and substituted derivatives; X = halogen) catalyze alkynes polymerization. In most cases one catalytic reaction predominates over the other possible routes, so that polymerization often takes place in the absence of oligomerization side reactions, and conversely cyclotrimerization is rarely accompanied by formation of either polyene or dimers. (C) 2009 Elsevier B. V. All rights reserved.
• Preparation of IrH(diene)L2 compounds via methoxyiridium complexes: Catalysts for hydrogen transfer reactions
  作者：Maria J. Fernandez、Miguel A. Esteruelas、Macarena Covarrubias、Luis A. Oro

  DOI：10.1016/0022-328x(86)80504-6

  日期：1986.12