[trans-bis(di-isopropyl-(1-methyl-4-tert-butylimidazol-2-yl)phosphine)Pd(methyl)(benzylamine)][tetrakis(pentafluorophenyl)borate] | 875439-40-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: [trans-bis(di-isopropyl-(1-methyl-4-tert-butylimidazol-2-yl)phosphine)Pd(methyl)(benzylamine)][tetrakis(pentafluorophenyl)borate]
• 英文别名: (4-tert-butyl-1-methylimidazol-2-yl)-di(propan-2-yl)phosphane;carbanide;palladium(2+);phenylmethanamine;tetrakis(2,3,4,5,6-pentafluorophenyl)boranuide
• CAS: 875439-40-0
• 化学式: C₂₄BF₂₀*C₃₆H₆₆N₅P₂Pd
• 分子量: 1416.36
• InChiKey: VRTJLIJIXPPYIS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.72
• 重原子数：
  89
• 可旋转键数：
  13
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  61.7
• 氢给体数：
  1
• 氢受体数：
  25

反应信息

• 作为产物：
  描述：

  4-(tert-butyl)-2-(diisopropylphosphino)-1-methyl-1H-imidazole 以 二氯甲烷 、 苯 为溶剂， 生成 [trans-bis(di-isopropyl-(1-methyl-4-tert-butylimidazol-2-yl)phosphine)Pd(methyl)(benzylamine)][tetrakis(pentafluorophenyl)borate]
  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