(2,6-((t-butyl)2PO)2C5H3N)IrCl | 1165815-13-3

• 英文名称: (2,6-((t-butyl)2PO)2C5H3N)IrCl
• 英文别名: (2,6-((t-butyl)₂PO)₂C₅H₃N)IrCl；[IrCl(2,6-bis(di-tert-butylphosphino)pyridine)]
• CAS: 1165815-13-3
• 化学式: C₂₁H₃₉ClIrNO₂P₂
• 分子量: 627.167
• InChiKey: RNYOEZQFHUTRJY-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：

  (2,6-((t-butyl)2PO)2C5H3N)IrCl 以 乙醚 、 甲苯 为溶剂， 生成 [Ir(CD3)(2,6-bis(di-tert-butylphosphino)pyridine)]
  参考文献：
  名称：

  Bernskoetter, Wesley H.; Hanson, Susan Kloek; Buzak, Sara K., Journal of the American Chemical Society, 2009, vol. 131, p. 8603 - 8613

  摘要：

  DOI：
• 作为产物：
  描述：

  [IrHCl(Me)(2,6-bis(di-tert-butylphosphino)pyridine)] 生成 (2,6-((t-butyl)2PO)2C5H3N)IrCl
  参考文献：
  名称：

  Mechanism of Hydrogenolysis of an Iridium–Methyl Bond: Evidence for a Methane Complex Intermediate

  摘要：

  Evidence for key a-complex intermediates in the hydrogenolysis of the iridium methyl bond of (PONOP)Ir(H)(Me)(+) (1) [PONOP = 2,6-bis(di-tert-butylphosphinito)pyridine] has been obtained. The initially formed eta(2)-H-2 complex, 2, was directly observed upon treatment of 1 with H-2, and evidence for reversible formation of a a-methane complex, 5, was obtained through deuterium scrambling from eta(2)-D-2 in 2-d(2) into the methyl group of 2 prior to methane loss. This sequence of reactions was modeled by density functional theory calculations. The transition state for formation of 5 from 2 showed significant shortening of the Ir-H bond for the hydrogen being transferred; no true Ir(V) trihydride intermediate could be located. Barriers to methane loss from 2 were compared to those of 1 and the six-coordinate species (PONOP)Ir(H)(Me)(CO)(+) and (PONOP)Ir(H)(Me)(Cl).

  DOI：

  10.1021/ja310982v

文献信息

• Dihydrogen Complexes of Iridium and Rhodium
  作者：Michael Findlater、Katherine M. Schultz、Wesley H. Bernskoetter、Alison Cartwright-Sykes、D. Michael Heinekey、Maurice Brookhart

  DOI：10.1021/ic202630x

  日期：2012.4.16

  interaction was probed using NMR spectroscopic studies. Complexes 1-H3, 2-H2, and 4-H2 retain the H–H bond and are classified as η2-dihydrogen adducts. In contrast, complex 3-H2 is best described as a classical dihydride system. The presence of bound dihydrogen was determined using both T1 and 1JHD coupling values: T1 = 14 ms, 1JHD = 33 Hz for the dihydrogen ligand in 1-H3, T1(min) = 23 ms, 1JHD = 32 Hz for

  合成了一系列铱和铑钳位配合物，并对其进行了表征：[（POCOP）Ir（H）（H 2）] [BARhref=https://www.molaid.com/MS_77868 target="_blank">BAr f 4 ]（1-H 3），（POCOP）Rh（H 2）（2- H 2），[（PONOP）Ir（C 2 H 4）] [BARhref=https://www.molaid.com/MS_77868 target="_blank">BAr f 4 ]（3-C 2 H 4），[（PONOP）Ir（H）2）] [BARhref=https://www.molaid.com/MS_77868 target="_blank">BAr f 4 ]（3-H 2），[（PONOP）Rh（C 2 H 4）] [BARhref=https://www.molaid.com/MS_77868 target="_blank">BAr f 4 ]（4-C 2 H 4）和[（PONOP）的Rh（H 2）] [BAR ˚F 4 ]（4-H 2）（POCOP =κ 3 -C 6 ħ 3 -2,6- [OP（吨丁基）2 ] 2 ; PONOP = 2,6-（t Bu 2 PO）2 C 5 H 3 N； BARhref=https://www.molaid.com/MS_77868 target="_blank">BAr f 4 =四（3,5-三氟甲基苯基）硼酸酯。使用NMR光谱学研究了二氢与金属相互作用的性质。络合物1-H 3， 2-H 2，和4-H 2保留H-H键和被分类为η
• Stability and Dynamic Processes in 16VE Iridium(III) Ethyl Hydride and Rhodium(I) σ-Ethane Complexes: Experimental and Computational Studies
  作者：Marc D. Walter、Peter S. White、Cynthia K. Schauer、Maurice Brookhart

  DOI：10.1021/ja4079539

  日期：2013.10.23

  Iridium(I) and rhodium(I) ethyl complexes, (PONOP)M(C2H5) (M = Ir (1-Et), Rh (2-Et)) and the iridium(I) propyl complex (PONOP)Ir(C3H7) (1-Pr), where PONOP is 2,6-(tBu2PO)2C5H3N, have been prepared. Low-temperature protonation of the Ir complexes yields the alkyl hydrides, (PONOP)Ir(H)(R) (1-(H)(Et)(+) and 1-(H)(Pr)(+)), respectively. Dynamic (1)H NMR characterization of 1-(H)(Et)(+) establishes site

  铱（I）和铑（I）乙基配合物，（PONOP）M（C2H5）（M = Ir（1-Et），Rh（2-Et））和铱（I）丙基配合物（PONOP）Ir（C3H7 ) (1-Pr)，其中 PONOP 是 2,6-(tBu2PO)2C5H3N，已制备。Ir 配合物的低温质子化产生烷基氢化物，(PONOP)Ir(H)(R)（1-(H)(Et)(+) 和 1-(H)(Pr)(+))，分别. 1-(H)(Et)(+) 的动态 (1)H NMR 表征建立了 Ir-H 和 Ir-CH2 质子之间的位点交换（ΔG(exH)(‡)(-110 °C) = 7.2(1) ) kcal/mol)，指向 σ-乙烷中间体。通过动态 (13)C NMR 光谱，测量了 α 和 β 碳（“链行走”）之间的交换势垒（ΔG(exC)(‡)(-110 °C) = 8.1(1) kcal/mol） . 乙烷损失的屏障为 17.4(1) kcal/mol
• A Cationic Terminal Methylene Complex of Ir(I) Supported by a Pincer Ligand
  作者：Jesus Campos、Riccardo Peloso、Maurice Brookhart、Ernesto Carmona

  DOI：10.1021/om400383s

  日期：2013.6.10

  rare example of a cationic methylene complex of Ir(I), [(PONOP)Ir(CH2)]+, 2 (PONOP = 2,6-bis(di-tert-butylphosphinito)pyridine), has been prepared by α-hydride abstraction from the previously described neutral methyl complex [(PONOP)Ir(CH3)]. The intrinsic high reactivity of the compound prevented both the isolation of a pure solid and its full characterization in the solid state. Nevertheless, the

  Ir（I）的阳离子亚甲基络合物的罕见实例[[（PONOP）Ir（CH 2）] +，2（PONOP = 2,6-双（二叔丁基膦基）吡啶）已通过α制备-从先前描述的中性甲基络合物[（PONOP）Ir（CH 3）]提取氢化物。该化合物固有的高反应活性既阻止了纯固体的分离，也阻止了其在固态状态下的全面表征。然而，建议的分子结构在多核NMR光谱学和反应性研究（包括与Lewis碱，二氢和重氮乙酸乙酯的反应）中得到了明确的支持。内鎓盐化合物，3，源于之间的反应[（PONOP）IR（CH 2）] +和PME 3，而η 2 -烯烃配合物5形成在涉及的亚甲基配体的C = C偶联反应2和重氮基乙酸乙酯。所述Ir═CH的氢解2的联动2导致了几个，先前已知的，氢化物和二氢铱络合物。