(1-(di-tert-butylphosphino)-3-tert-butylimidazol-2-ylidene) | 1354579-06-8

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (1-(di-tert-butylphosphino)-3-tert-butylimidazol-2-ylidene)
• 英文别名: 1-tert-butyl-3-[di(tert-butyl)phosphanyl]imidazol-2-ylidene；1-(di(tert-butyl)phosphanyl)-3-tert-butyl-imidazolylidene；ditert-butyl-(3-tert-butyl-2H-imidazol-3-ium-2-id-1-yl)phosphane
• CAS: 1354579-06-8
• 化学式: C₁₅H₂₉N₂P
• 分子量: 268.382
• InChiKey: IGVCKKZKFOOXEB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  (1-(di-tert-butylphosphino)-3-tert-butylimidazol-2-ylidene) 以 氘代苯 为溶剂， 反应 1.0h， 以98%的产率得到1-tert-butyl-2-[di(tert-butyl)phosphanyl]-1H-imidazole
  参考文献：
  名称：

  Direct synthesis of N-phosphanyl-heterocyclic carbenes

  摘要：

  A direct method for the synthesis of N-phosphanyl-heterocyclic carbenes is described. The method is based on the reaction of lithium imidazolides and benzimidazolides having a bulky alkyl group at the nitrogen atom with di(tert-butyl)chlorophosphine leading directly to the carbenes. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.11.054
• 作为产物：
  描述：

  1-叔丁基-1H-咪唑 在 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 25.0h， 生成 (1-(di-tert-butylphosphino)-3-tert-butylimidazol-2-ylidene)
  参考文献：
  名称：

  庞大的N-膦基官能化N-杂环碳烯配体：烯烃复分解的合成，钌配位化学和钌亚烷基络合物

  摘要：

  介绍了钌化学及其在基于N-膦基官能化的N-杂环卡宾配体（NHCP）的催化烯烃复分解中的应用。描述了烷基NHCP Ru的配位化学，并概述了将三甲基甲硅烷基和苯基亚烷基结合到钌亚烷基络合物的几种潜在合成前体中的方法。Ru亚烷基络合物被评估为潜在的烯烃复分解催化剂，并表现出潜在的性能。它们在升高的温度下显示出对于闭环易位和开环易位聚合的催化活性。

  DOI：

  10.1021/acs.inorgchem.5b00513

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
• Preparation and reactivity of a Ru(0) phosphino–carbene complex
  作者：Eliar Mosaferi、Li Pan、Tongen Wang、Yunshan Sun、Conor Pranckevicius、Douglas W. Stephan

  DOI：10.1039/c5dt04337a

  日期：——

  The reaction of the phosphino–carbene MeNC3H2NPtBu2 with RuHCl(CO)(PPh3)3 is shown to give facile access to the Ru(0) species (MeNC3H2NPtBu2)Ru(CO)(PPh3)2 (1). This species undergoes oxidative addition of H2 and silanes to give (MeNC3H2NPtBu2)RuH2(CO)(PPh3)24, (MeNC3H2NPtBu2)Ru H(SiRPh2)(CO)(PPh3) (R = Ph 5, H 6) and (MeNC3H2NPtBu2) RuH(PhSi(SCH2CH2)2O)(CO)(PPh3) 7.

  膦-卡宾MeNC 3 H 2 NP t Bu 2与RuHCl（CO）（PPh 3）3的反应表明，可以轻松地访问Ru（0）物种（MeNC 3 H 2 NP t Bu 2）Ru（ CO）（PPh 3）2（1）。该物质经过H 2和硅烷的氧化加成，得到（MeNC 3 H 2 NP t Bu 2）RuH 2（CO）（PPh 3）2 4，（MeNC 3H 2 NP t Bu 2）Ru H（SiRPh 2）（CO）（PPh 3）（R = Ph 5，H 6）和（MeNC 3 H 2 NP t Bu 2）RuH（PhSi（SCH 2 CH 2）2 O）（CO）（PPh 3）7。
• <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.