3-(di-tert-butyl-phosphanyl)-1-(2,4,6-trimethyl-phenyl)-imidazolin-2-ylidene | 1399855-25-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: 3-(di-tert-butyl-phosphanyl)-1-(2,4,6-trimethyl-phenyl)-imidazolin-2-ylidene
• 英文别名: (1-(di-tert-butylphosphino)-3-tert-butylimidazol-2-ylidene)；3-(di-tert-butylphosphino)-1-mesitylimidazol-2-ylidene；ditert-butyl-[3-(2,4,6-trimethylphenyl)-2H-imidazol-3-ium-2-id-1-yl]phosphane
• CAS: 1399855-25-4
• 化学式: C₂₀H₃₁N₂P
• 分子量: 330.453
• InChiKey: PLRABGGXXZYYGY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.55
• 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：

  3-(di-tert-butyl-phosphanyl)-1-(2,4,6-trimethyl-phenyl)-imidazolin-2-ylidene 以 氘代苯 为溶剂， 反应 0.25h， 生成
  参考文献：
  名称：

  N-phosphanyl-imidazolin-2-ylidenes: Novel stable carbenes as bidentate ligands for late transition metals

  摘要：

  N-phosphorylated, N-heterocyclic carbenes (NHC) based on the imidazoline skeleton have been prepared for the first time. The free carbenes feature good stability and in best cases they can be stored in the solid state for months at ambient temperature without decomposition. The carbenes are capable of acting as ligands towards late transition metal centres such as silver(l). The resulting complexes are stable and can be employed as reagents for the preparation of complexes of other group 11 metals upon transmetallation. The complexes, one carbene ligand and related compounds have all been structurally characterized. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2014.05.036
• 作为产物：
  描述：

  3-(di-tert-butylphosphino)-1-mesitylimidazolium triflate 在 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 1.5h， 以86%的产率得到3-(di-tert-butyl-phosphanyl)-1-(2,4,6-trimethyl-phenyl)-imidazolin-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

• Synthesis and Structures of Copper(I) Complexes with Phosphino-Functionalized N-Heterocyclic Carbenes (NHCP) and Bis-N-Heterocyclic Carbenes (Bis-NHC)
  作者：Erik Kühnel、Igor V. Shishkov、Frank Rominger、Thomas Oeser、Peter Hofmann

  DOI：10.1021/om300701u

  日期：2012.11.26

  New copper(I) complexes bearing N-phosphino- and N-phosphinomethyl-functionalized NHC ligands (NHCP systems) were synthesized and fully characterized. Using halide-containing copper(I) precursors, strikingly different structural motifs were found, dependent on the substitution pattern of the NHCP moiety. An interesting tetranuclear μ4-bridged copper(I) cluster (4b) is formed when CuBr·SMe2 is reacted

  合成并充分表征了带有N-膦基和N-膦基甲基官能化的NHC配体的新型铜（I）配合物。使用含卤化物的铜（I）前体，发现了完全不同的结构基序，具体取决于NHCP部分的取代方式。一个有趣的四核μ 4 -bridged铜（I）群集（图4b）时的CuBr·SMe的形成2与反应Ñ膦基取代的配体1A而双核配合物，图4a与类似的反应中形成1b中。双核金属环（2a，b）分离并通过X射线衍射对无卤化铜（I）前体[Cu（CH 3 CN）4 ] PF 6与NHCP配体1a，b使用N-膦酰基甲基取代的NHCP配体5a，b，以及分别使用双-NHC配体BIM和BIM-BMe 2（10a，b）。所观察到的铜（I）-铜（I）距离与所形成的金属环的大小直接相关。在10a，b中发现带电配合物对金属-金属分离有意想不到的强烈影响。直接使用Nt个步取代的配位体NHCP导致在铜（I）中心（形成一个电子不太有利的反式- C，C协调3和图
• Unexpected Reactivity Patterns of Ruthenium Alkylidenes with N-Phosphino-Functionalized N-Heterocyclic Carbene Ligands (NHCPs)
  作者：Christopher C. Brown、Philipp N. Plessow、Frank Rominger、Michael Limbach、Peter Hofmann

  DOI：10.1021/om5005429

  日期：2014.12.8

  N-phosphino-functionalized N-heterocyclic carbene (NHCP) ligands have been evaluated as potential supporting ligands in ruthenium-catalyzed olefin metathesis. Initial density functional theory (DFT) calculations suggested that these NHCP ligands may allow access to neutral 14 valence electron (VE) species—equivalents of the active 14 VE species formed by phosphine dissociation from Grubbs II precatalysts—via

  N-膦基官能化的N-杂环卡宾（NHCP）配体已被评估为钌催化烯烃复分解中的潜在支持配体。初始密度泛函理论（DFT）的计算表明，这些NHCP配体可以通过NHCP膦供体的易配位作用而获得中性14价电子（VE）种类-等效于通过磷化氢从Grubbs II前催化剂形成的活性14 VE种类。应变的四元[RuPNC]螯合物系统。他们尝试从NHCPs和Grubbs型Ru卡宾糖进行合成，发现在亚烷基片段上添加了NHCP供体原子（P或C），在五元螯合物结构中形成了一个新的C–P或C–C键。
• <i>N</i>-Phosphanyl- and <i>N</i>,<i>N</i>′-Diphosphanyl-Substituted N-Heterocyclic Carbene Chromium Complexes: Synthesis, Structures, and Catalytic Ethylene Oligomerization
  作者：Pengfei Ai、Andreas A. Danopoulos、Pierre Braunstein

  DOI：10.1021/acs.organomet.5b00547

  日期：2015.8.24

  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.