3-(di-tert-butylphosphino)-1-(2,6-di-isopropylphenyl)imidazol-2-ylidene | 1416734-73-0

• 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: 3-(di-tert-butylphosphino)-1-(2,6-di-isopropylphenyl)imidazol-2-ylidene
• 英文别名: (1-(di-tert-butylphosphino)-3-(2,6-diisopropylphenyl)imidazol-2-ylidene)；ditert-butyl-[3-[2,6-di(propan-2-yl)phenyl]-2H-imidazol-3-ium-2-id-1-yl]phosphane
• CAS: 1416734-73-0
• 化学式: C₂₃H₃₇N₂P
• 分子量: 372.534
• InChiKey: PHGWMIBFGDWICX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  6.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  氯化铬(II) 、 3-(di-tert-butylphosphino)-1-(2,6-di-isopropylphenyl)imidazol-2-ylidene 以 四氢呋喃 为溶剂， 以88%的产率得到[CrCl₂(^DippNHC,P-κC)₂]
  参考文献：
  名称：

  N-膦酰基和N，N'-二膦基取代的N-杂环碳铬配合物：合成，结构和催化乙烯低聚

  摘要：

  The chromium(II) complexes [CrCl2(t-BuNHC,P-kappa C)(2)] (1), [CrCl2((NHC)-N-Mes,P-kappa C)(2)] (2), [CrCl2((NHC)-N-Dipp,P-kappa C)(2)] (3), and [CrCl2(P,NHC,P-kappa C)(2)] (4) containing the N-phosphanyl- or N,N'-diphosphanyl-substituted N-heterocyclic carbene (NHC) hybrid ligands t-BuNHC,P (1-(di-tert-butylphosphino)-3-tert-butylimidazol-2-ylidene), (NHC)-N-Mes,P (1-(di-tert-butylphosphino)-3-mesitylimidazol-2-ylidene), (NHC)-N-Dipp,P (1-(di-tert-butylphosphino)-3-(2,6-diisopropylphenyl)imidazol-2-ylidene), and P,NHC,P (1,3-bis(di-tert-butylphosphino)imidazol-2-ylidene), respectively, were prepared from Cr-II ([CrCl2(thf)(2)]) or Cr-III ([CrCl3(thf)(3)] or [Cr(Me)Cl-2(thf)(3)]) precursors. The solid-state structures of these four complexes show square-planar Cr-II centers, with two trans chloride and two monodentate C-NHC donors. Alkylation of 3 and 4 with [Mg(benzyl)(2)(thf)(2)] led to the formation of the sigma complexes [Cr(benzyl)(3)((NHC)-N-Dipp,P-kappa C,kappa P)] (5) and [Cr(benzyl)(3)(P,NHC,P-kappa C,kappa P)] (6), respectively, with five-coordinate distorted-square-pyramidal Cr-III coordination, comprising a chelating ligand through the C-NHC and one P donor and three benzyl groups. These complexes were used as precatalysts in ethylene oligomerization, and it was found that the nature of the cocatalyst used and the metal oxidation state have a remarkable influence on the catalytic properties. The Cr-III/MAO systems displayed superior catalytic performance (TOF values up to 16320 mol of C2H4/((mol of Cr) h) for 6) and gave mostly oligomers. Interestingly, the oligomers obtained with complex 3 were almost exclusively 1-hexene and 1-butene when the reaction was initiated at 30 degrees C. The overall activities and selectivities were also affected by the initial reaction temperature and the nature of the solvent. With AlEtCl2 (EADC) as cocatalyst, polyethylene was predominately formed.

  DOI：

  10.1021/acs.organomet.5b00547
• 作为产物：
  描述：

  3-(di-tert-butylphosphino)-1-(2,6-di-isopropylphenyl)imidazolium triflate 在 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 1.0h， 以61%的产率得到3-(di-tert-butylphosphino)-1-(2,6-di-isopropylphenyl)imidazol-2-ylidene
  参考文献：
  名称：

  大量电子富集的N-磷酰基取代的N-杂环卡宾（NHCP配体）的过渡金属配合物。小咬角四元（κ- C，κ- P）螯合物结构

  摘要：

  庞大的，富电子的N-膦酰基取代的N-杂环卡宾（NHCP配体：Et CNP 3，Mes CNP 5a，Dipp CNP 5b）是潜在的配体，适用于应变很小的咬角四元过渡金属螯合物与（κ - ç，κ- P）金属配位。这种类型的各种化合物已被合成并充分表征尤其通过X射线晶体学。分离NHCP物种的反应3，图5a和5b中与适当的金属前体提供了一系列（κ- Ç（κ - P）配位的四元NHCP螯合物与镍三合会的金属和钌。该顺式-二甲基钯（II）配合物（的Mes CNP-κ Ç，κ- P）PDME 2（8）反应，在室温下与受主基取代的烯烃，如富马腈和马来酸酐，得到相应的η 2烯烃络合物9和10还原消除乙烷。Palladacyclopentadiene配合物11是通过炔烃-炔烃偶联将两个当量的二甲基乙炔二羧酸二甲酯添加到配合物8中而形成的。

  DOI：

  10.1021/om300963t

文献信息

• A Strategy to Control the Reactivation of Frustrated Lewis Pairs from Shelf‐Stable Carbene Borane Complexes
  作者：Yoichi Hoshimoto、Takuya Kinoshita、Masato Ohashi、Sensuke Ogoshi

  DOI：10.1002/anie.201505974

  日期：2015.9.28

  surrounding their carbene center through rotation of the phosphine oxide moiety. Either classical Lewis adducts (CLAs) or frustrated Lewis pairs (FLPs) are thus formed with B(C6F5)3 depending on the orientation of the phosphine oxide group. A strategy to reactivate FLPs from CLAs by exploiting molecular motions that are responsive to external stimuli has therefore been developed. The reactivation conditions

  已合成N-膦氧化物取代的咪唑基亚甲基（PoxIms）并进行了充分表征。这些物种可通过氧化膦部分的旋转对其卡宾中心周围的空间环境发生重大变化。因此，取决于氧化膦基团的取向，用B（C 6 F 5）3形成经典的路易斯加合物（CLA）或失意的路易斯对（FLP）。因此，已经开发出一种通过利用对外部刺激有响应的分子运动从CLA重新激活FLP的策略。通过调节PoxIm–B（C 6 F 5）3中的应变，成功控制了再活化条件 络合物，因此仅在高于环境温度的条件下才会发生再活化。
• Studies on Three-Coordinate [Co{N(SiMe₃)₂}₂L] Complexes, L = N-Heterocyclic Carbene
  作者：Alexandre Massard、Pierre Braunstein、Andreas A. Danopoulos、Sylvie Choua、Pierre Rabu

  DOI：10.1021/om501178p

  日期：2015.6.8

  A series of three-coordinate N-heterocyclic carbene bis(trimethylsilyl)amide complexes of cobalt, [CoN(SiMe3)(2)}(2)(NHC)] (NHC = N,N'-diarylimidazolin-2-ylidene, aryl = 2,6-diisopropylphenyl, SIPr (1), aryl = mesityl, SIMes (2); kappa(1)-N,N'-diphosphanylimidazol-2-ylidene, PCP (5); kappa(1)-N-phosphanyl-N'-2,6-diisopropylphenylimidazol-2-ylidene, PC (6); cyclic alkyl amino carbehe :C(Cy)CH2CMe2N-2,6Pr(2)(i)C(6)H(3), cAAC(Cy) (7)) were prepared by the reaction of [CoN(SiMe3)(2)}(2)] with the corresponding NHCs. The complexes exhibited interesting transamination reactivity in reactions with bulky 2,6-diisopropylaniline (NH2(DiPP)), where adjustment of the stoichiometry and reaction conditions resulted in the substitution of one or two N(SiMe3)(2) ligands by the anilido ligand NH(DiPP), giving [CoN(SiMe3)(2)}NH(DiPP)}(NHC)] (NHC = N,N'-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, IPr (8)) and [CoNH(DiPP)}(2)(NHC)] (NHC = SIPr (9); IPr (10); PCP (11)). X-ray crystallography revealed trigonal-planar coordination geometry at Co for all of the new complexes and long Co-C-NHC bond lengths; in the cases of 5, 8, 9, 10, and 11, intramolecular Co ... H and/or H ... P interactions may provide further stabilization of specific conformations. Magnetic and electron paramagnetic resonance studies showed that the three-coordinate Co(II) centers in 1-7 behave as S = 3/2 spins with strong anisotropy arising from the low symmetry of the coordination site (C-2v). The anisotropy results in large values of the zero-field splitting parameter D.