N,N'-Bis(2,2-dimethylpropyl)benzimidazolin-2-ylidene | 227103-01-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并咪唑类
• 英文名称: N,N'-Bis(2,2-dimethylpropyl)benzimidazolin-2-ylidene
• 英文别名: N,N'-bis(2,2-dimethylpropyl)benzimidazol-2-ylidene；1,3-di-neopentyl-benzimidazol-2-ylidene；1,3-dineopentyl-benzimidazol-2-ylidene；1,3-bis(2,2-dimethylpropyl)-2H-benzimidazol-3-ium-2-ide
• CAS: 227103-01-7
• 化学式: C₁₇H₂₆N₂
• 分子量: 258.407
• InChiKey: ZPLKMNQZJJGPDG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 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：

  2,2-二甲基丙基次基膦 、 N,N'-Bis(2,2-dimethylpropyl)benzimidazolin-2-ylidene 以 氘代苯 为溶剂， 反应 48.0h， 以92%的产率得到2-[1-(3,5-Ditert-butyl-1,2,4-triphosphol-1-yl)-2,2-dimethylpropylidene]-1,3-bis(2,2-dimethylpropyl)benzimidazole
  参考文献：
  名称：

  Novel 1,2,4-Triphosphole and 1,2,3-Triphosphetene Derivatives fromN,N′-Bis(2,2-dimethylpropyl)benzimidazolin-2-ylidene and Phosphaalkynes

  摘要：

  DOI：

  10.1002/1521-3773(20000703)39:13<2307::aid-anie2307>3.0.co;2-d
• 作为产物：
  描述：

  1,3-dineopentyl-benzimidazolium hexafluorophosphate 在 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 N,N'-Bis(2,2-dimethylpropyl)benzimidazolin-2-ylidene
  参考文献：
  名称：

  Ligand bending and tilted coordination in the coordinatively unsaturated NHC complex lateral-bis(N,N′-dineopentyl-benzimidazoline-2-ylidene)molybdenumtricarbonyl – Synthesis and structural investigations

  摘要：

  Reaction of free dineopentyl-benzimidazoline-2-ylidene 1 (ligand: np2bimy) with (eta(3)-cycloheptatriene) Mo(CO)(3), molar ratio 3:1, provides the coordinatively unsaturated lateral-(np(2)bimy)(2)Mo(CO)(3) complex 2. Crystal structure analysis of 2 reveals an almost ideal cis-square pyramidal geometry with tilted coordination of the metal, interplanar angles of the np2bimy ligands to the C4Mo plane of about 70 degrees and significant bending of the N-heterocyclic carbene rings towards each other. Quantum chemical calculations (B97-D/6-31G(d)[Mo:cc-pVTZ-PP] level of theory) reproduce this peculiar structure and show it to be more stable by 36 kJ/mol than the second energy-minimum structure with trigonal bipyramidal geometry and the carbene ligands in the axial positions. Calculations indicated no significant Mo-C(II) back-bonding or interactions of the empty d-orbital with adjacent p-orbitals of the ligands, implying that the ligand distortions, tilted coordination and the occurrence of a free coordination site are caused by the spatial demand of the N-substituents. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2015.01.014

文献信息

• Donor−Acceptor Triazenes:  Synthesis, Characterization, and Study of Their Electronic and Thermal Properties
  作者：Dimitri M. Khramov、Christopher W. Bielawski

  DOI：10.1021/jo070789x

  日期：2007.12.1

  to slowly decompose at room temperature. Triazenes featuring electron-rich phenyl azide components decomposed at higher temperatures than their electron-deficient analogues. Products of the thermally induced triazene decomposition reaction were identified as molecular nitrogen and the respective guanidine. Using an isotopically labeled triazene, the mechanism of the decomposition reaction was found

  通过将官能化的苯并咪唑-2-亚烷基以游离N-杂环卡宾或从其各自的苯并咪唑鎓前体原位生成的各种官能化苯甲酰胺与适量的分离出的芳基叠氮化物偶合（ 36-99％）。使用紫外可见光谱，核磁共振光谱和X射线晶体学研究了两个耦合组分之间的电子离域。根据N-杂环卡宾和有机叠氮化物上官能团的互补性，发现各自的三氮烯显示出λmax值在364至450 nm之间。X射线晶体学揭示了一系列供体-受体化合物特有的三氮烯中的键改变模式。使用热重分析法研究了三氮烯的热稳定性，发现三氮烯的热稳定性强烈依赖于苯并咪唑-2-亚烷基组分的空间和叠氮化物组分的电子学。三氮烯具有庞大的N取代基（例如，新戊基，叔丁基-丁基等）在超过150°C的温度下在固态下稳定，而具有小的N-取代基（例如甲基）的类似物在室温下会缓慢分解。具有富电子叠氮化物成分的三氮烯比其缺乏电子的类似物在更高的温度下分解。热诱导的三氮烯分解反应的产物被鉴定为分子氮
• Crystalline (NN)C–M(NN) complexes: synthesis, structure, bonding and lability [M = Si, Ge, Sn or Pb; (NN) = 1,2-(ButCH2N)2C6H4]
  作者：Barbara Gehrhus、Peter B. Hitchcock、Michael F. Lappert

  DOI：10.1039/b005216g

  日期：——

  Each of the red-brown or red, isomorphous, crystalline adducts (NN)C–M(NN) [(NN) = 1,2-(ButCH2N)2C6H4 and M = Si, Ge, Sn or Pb] has been obtained from the carbene (NN)C and the appropriate silylene, germylene, stannylene or plumbylene M(NN) in benzene and crystallisation from a hydrocarbon. They are monomeric, with the three-co-ordinate Ccarb and M atoms in an almost planar (C) or pyramidal (M) environment. The C–M distances are more than ca. 10% longer than for a typical MII–C bond in an MR2 molecule. Variable temperature 13C and xM NMR spectra (xM = 29Si, 119Sn or 207Pb) in toluene-d8, as well as for the appropriate M(NN) and C(NN) precursors, have been recorded. The Ccarb and M chemical shift data show that the compounds readily dissociate in solution, their stability decreasing in the sequence Sn > Pb > Si > Ge. From the magnitude of the chemical shifts, their conformation and C–M distances of the adducts, it is concluded that the C–M bond in each adduct is best formulated as being electrostatic in nature, with the carbene moiety as electron donor and the M(NN) fragment as acceptor.

  每个红棕色或红色同晶结晶加合物 (NN)C→M(NN) [(NN) = 1,2-(ButCH2N)2C6H4 且 M = Si、Ge、Sn 或 Pb]由卡宾 (NN)C 和适当的亚甲硅基、甲亚甲基、亚锡基或铅亚甲基 M(NN) 在苯中以及从烃中结晶而获得。它们是单体，三配位的 Ccarb 和 M 原子处于几乎平面 (C) 或金字塔形 (M) 环境中。 C–M 距离超过约。比 MR2 分子中典型的 MII-C 键长 10%。记录了甲苯-d8 中以及适当的 M(NN) 和 C(NN) 前体的变温 13C 和 xM NMR 谱（xM = 29Si、119Sn 或 207Pb）。 Ccarb 和 M 化学位移数据表明，化合物在溶液中容易解离，其稳定性按 Sn > Pb > Si > Ge 的顺序递减。从化学位移的大小、加合物的构象和 C–M 距离可以得出结论，每个加合物中的 C–M 键最好表述为静电性质，其中卡宾部分作为电子供体， M(NN) 片段作为受体。
• Novel highly electron-deficient quinoxaline-annulated 1,3,2-diazagermol- and diazastannol-2-ylidenes, stabilized as LiCl adducts
  作者：Farman Ullah、Olaf Kühl、Wajid Rehman、Peter G. Jones、Joachim Heinicke

  DOI：10.1016/j.poly.2009.12.014

  日期：2010.2

  Reaction of 2,3-bis(neopentylamino)quinoxaline ( 1 ) with n BuLi and GeCl 4 or GeCl 2 ·(dioxane) (molar ratio 1:2:1) in THF furnished highly moisture-sensitive Ge(IV) and Ge(II) heterocycles 2a and 3a , respectively. The quinoxaline-annulated N -heterocyclic germylene (quinNHGe) 3a is stable only in the presence of Li(THF) x and exhibits electrophilic properties associated with the strongly electron-withdrawing

  2,3-双（新戊基氨基）喹喔啉（1）与n BuLi和GeCl 4或GeCl 2·（二恶烷）（摩尔比为1：2：1）在THF中的反应提供了高度湿敏的Ge（IV）和Ge（IV II）分别为杂环2a和3a。喹喔啉环化的N-杂环亚二甲基（quinNHGe）3a仅在Li（THF）x存在下才稳定，并且表现出与强吸电子环化相关的亲电性能。如在双（喹喔啉）环化的八元NHGe LiCl加合物的晶体中发现的，假定Ge（II）处的氯化物与N处的Li +发生配位。如对于卡宾供体原子的NMR信号的强下场配位位移所表明的，二烯戊基-苯并咪唑-2-亚烷基（bnNHC）的添加提供了不稳定的bnNHC-quinNHGe加合物4。试图生长单晶导致卡宾分解和质子化，从而与Li 2（THF）2 Cl 4 2-阴离子形成双（苯并咪唑鎓）盐5。将2-甲氧基乙基或2-二甲基氨基乙基侧链作为螯合官能团引入二氨基喹喔啉6和7中，然后与2 n
• The Ti(IV) Complex of a Benzannulated N-Heterocyclic Carbene
  作者：F. Ekkehardt Hahn、Thorsten von Fehren、Roland Fröhlich

  DOI：10.1515/znb-2004-0321

  日期：2004.3.1

  The yellow titanium(IV) carbene complex [TiCl₄(1)], 2 (1 = N,N’-bis(2,2-dimethylpropyl)benzimidazol-2-ylidene) was synthesized by reaction of TiCl₄ and the benzannulated carbene 1 in toluene. The X-ray structure analysis revealed a mononuclear complex with a titanium(IV) center coordinated in a distorted trigonal-bipyramidal fashion by the carbene ligand in an equatorial position and four chloro ligands

  黄色的钛(IV)卡宾配合物[TiCl₄(1)]，2 (1 = N,N'-双(2,2-二甲基丙基)苯并咪唑-2-基亚甲基)是通过在甲苯中反应TiCl₄和苯并环卡宾1合成的。X射线结构分析显示，这是一个单核配合物，其中钛(IV)中心以扭曲的三角双锥方式被位于赤道位置的卡宾配体和四个氯配体配位。
• N,N′-Bis(2,2-dimethylpropyl)benzimidazolin-2-ylidene: A Stable Nucleophilic Carbene Derived from Benzimidazole
  作者：F. Ekkehardt Hahn、Lars Wittenbecher、Roland Boese、Dieter Bläser

  DOI：10.1002/(sici)1521-3765(19990604)5:6<1931::aid-chem1931>3.0.co;2-m

  日期：1999.6.4