di-tert-butyl-(1-methylimidazol-2-yl)phosphine | 875439-09-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: di-tert-butyl-(1-methylimidazol-2-yl)phosphine
• 英文别名: 2-[di(tert-butyl)phosphino]-1-methyl-1H-imidazole；Ditert-butyl-(1-methylimidazol-2-yl)phosphane；ditert-butyl-(1-methylimidazol-2-yl)phosphane
• CAS: 875439-09-1
• 化学式: C₁₂H₂₃N₂P
• 分子量: 226.302
• InChiKey: UWMOBSWIBVSKOB-UHFFFAOYSA-N

物化性质

• 沸点：
  301.6±25.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  17.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  di-tert-butyl-(1-methylimidazol-2-yl)phosphine 以 苯 为溶剂， 生成 [(di-tert-butyl-(1-methyl-imidazol-2-yl)phosphine)2Pd(methyl)][triflate]
  参考文献：
  名称：

  Changes in Coordination of Sterically Demanding Hybrid Imidazolylphosphine Ligands on Pd(0) and Pd(II)

  摘要：

  Low-coordinate organometallic complexes are important in structure and catalysis, and hemilability or secondary interactions such as hydrogen bonding enabled by hybrid ligands are receiving increasing attention. To study the factors controlling these phenomena, three new imidazol-2-ylphosphine ligands, L, were made. In these ligands, the bulk around P and the hindrance at the basic and potentially coordinating imidazole N-3 were varied. Remarkably, L2Pd(0) complexes 3a-c were shown to be two-coordinate, 12-electron species, despite the availability of imidazole N-3 to enter into eta(2)-P,N chelation. In oxidative additions of C-X bonds to the Pd(0) complexes, reaction rates and products could be controlled by the nature of the C and X groups and the R groups on the phosphine. Most significantly, whereas 4c-Phl and 4c-MeOTf from 3c are normal trans-bis(phosphine)Pd(R)(X) species, 5a-Phl, 5a-PhBr, and 5b-Phl from 3a and 3b were shown by X-ray diffraction to be a monomeric species with a single eta(2)-P,N-chelating phosphine. From 3a and methyl triflate, an ionic complex [6a-Me](+)[OTf](-) with one chelating and one nonchelating phosphine was formed, with temperature-dependent windshield-wiper exchange of the two, showing hemilability. Thus, large phosphine substituents (R = tert-butyl rather than isopropyl) favor chelation. The chelate Pd-imidazole N-3 bond is longer when the heterocyclic nitrogen is hindered by an adjacent tert-butyl group at C-4 (comparing 5a-Phl and 5b-Phl). Finally, whereas in [8b-Ph](+)[OTf](-) from 5b-Phl and isopropylamine, the amine coordinates without chelate opening or hydrogen bonding, in [10c-Me](+)[OTf](-) made from 4c-MeOTf and isopropylamine, the amine is not only coordinated at N but also donates a hydrogen bond to each phosphine imidazol-2-yl substituent.

  DOI：

  10.1021/ja054779u
• 作为产物：
  描述：

  1-(di(tert-butyl)phosphino)-3-methyl-Imidazol-2-ylidene 以 氘代苯 为溶剂， 反应 1.0h， 以60%的产率得到di-tert-butyl-(1-methylimidazol-2-yl)phosphine
  参考文献：
  名称：

  N-磷酸化的咪唑鎓盐作为2和5磷酸化的咪唑和具有PNCN单元的新型咪唑-2-亚胺的前体

  摘要：

  实验已经证明1-或1，2-二取代的咪唑与二有机基磷（III）卤化物的反应是通过最初形成N-磷酸化的咪唑鎓盐而进行的。用强碱处理这些盐会相应地导致母体咪唑在2或5位发生磷酸化。在先前的情况下，形成咪唑-2-亚基作为中间体。在N1和N3原子上都带有空间要求或/和π供体基团的情况下，将1,3-二取代的咪唑鎓盐与NaN（SiMe 3）2进行去质子化反应可得到新的稳定的N-磷取代的Arduengo型卡宾。

  DOI：

  10.1021/jo101177h

文献信息

• Bifunctional Imidazolylphosphine Ligands as Hydrogen Bond Donors Promote N−H and O−H Activation on Platinum
  作者：Douglas B. Grotjahn、Yi Gong、Antonio G. DiPasquale、Lev N. Zakharov、Arnold L. Rheingold

  DOI：10.1021/om060880b

  日期：2006.11.1

  The NH moieties of two imidazolylphosphine ligands on Pt(II) facilitate formation of trans-(hydrido)((RO)-O-1) bis-(phosphine) Pt(II) species from (ROH)-O-1 (R-1 = CF3CO, CH3CO, Ph, CH3, H). Evidence points to formation of a reliable binding pocket for coordinated (RO)-O-1 by hydrogen bond donation from the two NH groups.
• VERFAHREN ZUR CARBONYLIERUNG VON OLEFINEN
  申请人：Evonik Degussa GmbH

  公开号：EP2951143B1

  公开（公告）日：2016-11-30
• N-Phosphorylated Imidazolium Salts as Precursors to 2- and 5-Phosphorylated Imidazoles and New Imidazol-2-ylidenes Featuring the PNCN Unit
  作者：Anatolii P. Marchenko、Heorgii N. Koidan、Anastasiya N. Huryeva、Evgeniy V. Zarudnitskii、Aleksandr A. Yurchenko、Aleksandr N. Kostyuk

  DOI：10.1021/jo101177h

  日期：2010.11.5

  It has been experimentally proven that the reaction of 1- or 1,2-disubstituted imidazoles with diorganylphosphorus(III) halides proceeds via initial formation of N-phosporylated imidazolium salts. Treatment of these salts with strong bases results in phosphorylation of the parent imidazoles at the 2- or 5-positions, correspondingly. In a previous case, imidazol-2-ylidenes are formed as intermediates

  实验已经证明1-或1，2-二取代的咪唑与二有机基磷（III）卤化物的反应是通过最初形成N-磷酸化的咪唑鎓盐而进行的。用强碱处理这些盐会相应地导致母体咪唑在2或5位发生磷酸化。在先前的情况下，形成咪唑-2-亚基作为中间体。在N1和N3原子上都带有空间要求或/和π供体基团的情况下，将1,3-二取代的咪唑鎓盐与NaN（SiMe 3）2进行去质子化反应可得到新的稳定的N-磷取代的Arduengo型卡宾。
• Changes in Coordination of Sterically Demanding Hybrid Imidazolylphosphine Ligands on Pd(0) and Pd(II)
  作者：Douglas B. Grotjahn、Yi Gong、Lev Zakharov、James A. Golen、Arnold L. Rheingold

  DOI：10.1021/ja054779u

  日期：2006.1.1

  Low-coordinate organometallic complexes are important in structure and catalysis, and hemilability or secondary interactions such as hydrogen bonding enabled by hybrid ligands are receiving increasing attention. To study the factors controlling these phenomena, three new imidazol-2-ylphosphine ligands, L, were made. In these ligands, the bulk around P and the hindrance at the basic and potentially coordinating imidazole N-3 were varied. Remarkably, L2Pd(0) complexes 3a-c were shown to be two-coordinate, 12-electron species, despite the availability of imidazole N-3 to enter into eta(2)-P,N chelation. In oxidative additions of C-X bonds to the Pd(0) complexes, reaction rates and products could be controlled by the nature of the C and X groups and the R groups on the phosphine. Most significantly, whereas 4c-Phl and 4c-MeOTf from 3c are normal trans-bis(phosphine)Pd(R)(X) species, 5a-Phl, 5a-PhBr, and 5b-Phl from 3a and 3b were shown by X-ray diffraction to be a monomeric species with a single eta(2)-P,N-chelating phosphine. From 3a and methyl triflate, an ionic complex [6a-Me](+)[OTf](-) with one chelating and one nonchelating phosphine was formed, with temperature-dependent windshield-wiper exchange of the two, showing hemilability. Thus, large phosphine substituents (R = tert-butyl rather than isopropyl) favor chelation. The chelate Pd-imidazole N-3 bond is longer when the heterocyclic nitrogen is hindered by an adjacent tert-butyl group at C-4 (comparing 5a-Phl and 5b-Phl). Finally, whereas in [8b-Ph](+)[OTf](-) from 5b-Phl and isopropylamine, the amine coordinates without chelate opening or hydrogen bonding, in [10c-Me](+)[OTf](-) made from 4c-MeOTf and isopropylamine, the amine is not only coordinated at N but also donates a hydrogen bond to each phosphine imidazol-2-yl substituent.