[(2,6-bis-(di-tert-butylphosphinomethyl)pyridine)Ir(C₆H₅)] | 918344-64-6

• 英文名称: [(2,6-bis-(di-tert-butylphosphinomethyl)pyridine)Ir(C₆H₅)]
• 英文别名: [(^tBuPNP)Ir(C₆H₅)]；phenyl(2,6-bis(di-tert-butylphosphinomethyl)pyridine)iridium(I)；(2,6-bis((di-tert-butylphosphino)methyl)pyridine)Ir(I)(C6H5)
• CAS: 918344-64-6
• 化学式: C₂₉H₄₈IrNP₂
• 分子量: 664.874
• InChiKey: QECQJMNRBALCDU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  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-bis-(di-tert-butylphosphinomethyl)pyridine)Ir(C₆H₅)] 以 氘代甲苯 为溶剂， 生成
  参考文献：
  名称：

  O₂ Activation by Metal–Ligand Cooperation with Ir^I PNP Pincer Complexes

  摘要：

  A unique mode of molecular oxygen activation, involving metal-ligand cooperation, is described. Ir pincer complexes [((BuPNP)-Bu-t)Ir(R)] (R = C6H5 (1), CH2COCH3 (2)) react with O-2 to form the dearomatized hydroxo complexes [((BuPNP)-Bu-t*)Ir(R)(OH)] ((t)BuPNP* = deprotonated (BuPNP)-Bu-t ligand), in a process which utilizes both O-atoms. Experimental evidence, including NMR, EPR, and mass analyses, indicates a binuclear mechanism involving an O-atom transfer by a peroxo intermediate.

  DOI：

  10.1021/jacs.5b01585
• 作为产物：
  描述：

  hydrido(2,6-bis(di-tert-butylphosphinomethyl)pyridine)phenyliridium(I) hexafluorophosphate 在 t-BuOK 作用下， 以 四氢呋喃 为溶剂， 生成 [(2,6-bis-(di-tert-butylphosphinomethyl)pyridine)Ir(C₆H₅)]
  参考文献：
  名称：

  Metal−Ligand Cooperation in C−H and H₂ Activation by an Electron-Rich PNP Ir(I) System:  Facile Ligand Dearomatization−Aromatization as Key Steps

  摘要：

  Unusual reactions are reported, in which the aromatic PNP ligand (PNP = 2,6-bis-(di-tert-butylphosphinomethyl)pyridine) acts in concert with the metal in the activation of H2 and benzene, via facile aromatization/dearomatization processes of the ligand. A new, dearomatized electron-rich (PNP*)Ir(I) complex 2 (PNP* = deprotonated PNP) activates benzene to form the aromatic (PNP)Ir(I)Ph 4, which upon treatment with CO undergoes a surprising oxidation process to form (PNP*)Ir(III)(H)CO 6, involving proton migration from the ligand "arm" to the metal, with concomitant dearomatization. 4 undergoes stereoselective activation of H2 to exclusively form the trans-dihydride 7, rather than the expected cis-dihydride complex. Our evidence, including D-labeling, suggests the possibility that the Ir(I)-Ph complex is transformed to the dearomatized Ir(III)(Ph)(H) (independently prepared at low temperature), which may be the actual intermediate undergoing H2 activation.

  DOI：

  10.1021/ja066411i

文献信息

• Synthesis and Reactivity of an Iridium(I) Acetonyl PNP Complex. Experimental and Computational Study of Metal−Ligand Cooperation in H−H and C−H Bond Activation via Reversible Ligand Dearomatization
  作者：Leonid Schwartsburd、Mark A. Iron、Leonid Konstantinovski、Yael Diskin-Posner、Gregory Leitus、Linda J. W. Shimon、David Milstein

  DOI：10.1021/om1004435

  日期：2010.9.13

  actually activates H2 to exclusively form the trans-dihydride (PNP)IrIII(H)2(CH2COCH3) (5a) and activates D2 to form the trans-hydride−deuteride 5b with benzylic-D incorporation, as also corroborated by DFT studies. Interestingly, benzene C−H activation by complex 2 results in formation of the complex (PNP)IrI(C6H5) (6a) and elimination of acetone. DFT studies show that the benzene C−H bond is actually

  配合物（PNP）Ir I（CH 2 COCH 3）2（PNP = 2,6-双（（二叔丁基膦基）甲基）吡啶）是通过脱芳香化的富电子配合物（PNP *）反应制得的Ir 1（COE）（1 ; PNP * =去质子化的PNP，COE =环辛烯）与丙酮。在用CO处理后，配合物2经历了令人惊讶的丙酮消除，从而形成了脱芳构化的物种（PNP *）Ir I（CO）（4），涉及质子从配体“臂”迁移到丙酮基部分。DFT研究表明，该过程是通过方形锥体中间体2 + CO发生的，该中间体是由CO配位形成参见图2，其中丙酮基部分在质子迁移之前位于顶端位置。的反应2用H 2（d 2）表示复之间的平衡2和非芳族（PNP *）IR III（H）（CH 2 COCH 3）复合物2b中，这是实际激活小时物种2为排他性地形成反式二氢化物（PNP）Ir III（H）2（CH 2 COCH 3）（5a）并活化D 2形成反式氢化物-氘代
• Formal oxidative addition of a C–H bond by a 16e iridium(<scp>i</scp>) complex involves metal–ligand cooperation
  作者：Amit Kumar、Moran Feller、Yehoshoa Ben-David、Yael Diskin-Posner、David Milstein

  DOI：10.1039/c8cc01885e

  日期：——

  The first example of oxidative addition of a C–H bond to a square planar d8-Iridium complex, without any external additive, such as an acid, is described. Our mechanistic investigations show that metal–ligand cooperation through aromatization–dearomatization of the lutidine backbone is involved in this process, and that the actual C–H activation step occurs through an Ir(III) intermediate.

  描述了在没有任何外部添加剂（例如酸）​​的情况下将C–H键氧化加成至方形平面d8-铱配合物的第一个例子。我们的机理研究表明，该过程涉及通过二甲基吡啶骨架的芳构化-脱芳构化而进行的金属-配体协同作用，而实际的CH-H活化步骤是通过Ir（III）中间体进行的。
• CO₂ activation by metal<b>−</b>ligand-cooperation mediated by iridium pincer complexes
  作者：Moran Feller、Eyal Ben-Ari、Yael Diskin-Posner、David Milstein

  DOI：10.1080/00958972.2018.1475662

  日期：2018.7.3

  activation of CO2 by the dearomatized complex [(tBuPNP*)Ir(COE)] (1) and by the aromatized complex [(tBuPNP)Ir(C6H5)] (2) via metal-ligand cooperation (MLC) (tBuPN = 2,6-bis-(di-tert-butylphosphinomethyl)pyridine; tBuPNP* = deprotonated PNP; COE = cyclooctadiene). The [1,3]-addition of CO2 to 1 and 2 is reversible at ambient temperature. While the dearomatized complex 1 reacts readily at ambient temperature

  摘要 在此我们报告了脱芳构化络合物 [(tBuPNP*)Ir(COE)] (1) 和芳构化络合物 [(tBuPNP)Ir(C6H5)] (2) 通过金属配体合作 (MLC) 对 CO2 的可逆活化) (tBuPN = 2,6-双-(二叔丁基膦甲基)吡啶；tBuPNP* = 去质子化的 PNP；COE = 环辛二烯)。 向 1 和 2 的 [1,3]-加成在环境温度下是可逆的。脱芳构化配合物 1 在环境温度下很容易与 THF 或苯中的 反应，而配合物 2 在苯中于 80 °C 或环境温度下在 THF 中加热时与 反应。新型芳构化复合物 [(tBuPNP)IrCl] (10) 不与 反应。基于 1、2 和 10 与 的反应模式，我们建议通过 MLC 的 活化仅通过脱芳构化物种发生，