(2,6-bis(di-tert-butylphosphinito)pyridine)Ir(CH3) | 1165815-20-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2,6-bis(di-tert-butylphosphinito)pyridine)Ir(CH3)
• 英文别名: [IrMe(2,6-bis(di-tert-butylphosphinito)pyridine)]；[IrMe(2,6-bis(di-tert-butylphosphino)pyridine)]；[Ir(PONOP)Me]
• CAS: 1165815-20-2
• 化学式: C₂₂H₄₂IrNO₂P₂
• 分子量: 606.748
• InChiKey: QVRWPNNUBZUDNZ-UHFFFAOYSA-N

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：

  (2,6-bis(di-tert-butylphosphinito)pyridine)Ir(CH3) 、 氢气 以 benzene-d6 为溶剂， 生成 (2,6-bis(di-tert-butylphosphinito)pyridine)Ir(CH3)H2
  参考文献：
  名称：

  Proton-Catalyzed Hydrogenation of a d⁸ Ir(I) Complex Yields a trans Ir(III) Dihydride

  摘要：

  Hydrogenation of the (PONOP)Ir(I)CH3 complex [PONOP = 2,6-bis(di-tert-butylphosphinito)pyridine] yields the unexpected trans-dihydride species (PONOP)IICH3(H)(2). Mechanistic investigations have revealed that this reaction proceeds via proton-catalyzed H-2 cleavage, a pathway that circumvents the intermediacy of the typically invoked cis-dihydride isomer. Protonation yields the cationic (PONOP)Ir(CH3)(H). complex, which is then trapped by H-2 to yield an eta(2)-H-2 complex. Deprotonation of this species yields the trans-dihydride. Intermediates in the proposed pathway have been confirmed by independent low-temperature syntheses and spectroscopic observations.

  DOI：

  10.1021/ja100168w
• 作为产物：
  描述：

  (2,6-bis(di-tert-butylphosphinito)pyridine)Ir(CH3)H2 以 benzene-d6 为溶剂， 生成 (2,6-bis(di-tert-butylphosphinito)pyridine)Ir(CH3)
  参考文献：
  名称：

  Proton-Catalyzed Hydrogenation of a d⁸ Ir(I) Complex Yields a trans Ir(III) Dihydride

  摘要：

  Hydrogenation of the (PONOP)Ir(I)CH3 complex [PONOP = 2,6-bis(di-tert-butylphosphinito)pyridine] yields the unexpected trans-dihydride species (PONOP)IICH3(H)(2). Mechanistic investigations have revealed that this reaction proceeds via proton-catalyzed H-2 cleavage, a pathway that circumvents the intermediacy of the typically invoked cis-dihydride isomer. Protonation yields the cationic (PONOP)Ir(CH3)(H). complex, which is then trapped by H-2 to yield an eta(2)-H-2 complex. Deprotonation of this species yields the trans-dihydride. Intermediates in the proposed pathway have been confirmed by independent low-temperature syntheses and spectroscopic observations.

  DOI：

  10.1021/ja100168w

文献信息

• Large Kinetic Isotope Effects for the Protonolysis of Metal–Methyl Complexes Are Not Reliable Mechanistic Indicators
  作者：Valerie J. Scott、Jay A. Labinger、John E. Bercaw

  DOI：10.1021/om200432b

  日期：2011.8.22

  several palladium and platinum methyl complexes (with release of methane) had suggested the possibility that observation of an unusually large kinetic isotope effect, consistent with significant contributions from quantum mechanical tunneling, might be diagnostic of a mechanism involving direct protonation of the metal–methyl bond, as opposed to one proceeding via a metal hydride intermediate. By extension

  早期对几种钯和铂甲基配合物（释放甲烷）进行质子水解的研究表明，观察到异常大的动力学同位素效应（与量子机械隧穿的重大贡献相一致）可能是诊断涉及直接质子化的机理的可能性。金属-甲基键，与通过金属氢化物中间体进行的操作相反。通过将这些度量扩展到更广泛的复合体，我们发现不支持所提出的相关性。
• 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。
• Bernskoetter, Wesley H.; Hanson, Susan Kloek; Buzak, Sara K., Journal of the American Chemical Society, 2009, vol. 131, p. 8603 - 8613
  作者：Bernskoetter, Wesley H.、Hanson, Susan Kloek、Buzak, Sara K.、Davis, Zoe、White, Peter S.、et al.

  DOI：——

  日期：——
• Mechanism of Hydrogenolysis of an Iridium–Methyl Bond: Evidence for a Methane Complex Intermediate
  作者：Jesús Campos、Sabuj Kundu、Dale R. Pahls、Maurice Brookhart、Ernesto Carmona、Thomas R. Cundari

  DOI：10.1021/ja310982v

  日期：2013.1.30

  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).