N-(2-bromo-4-tert-butylbenzyl)-1-(pyridine-2-yl)-N-(pyridine-2-ylmethyl)methanamine | 1191437-58-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-(2-bromo-4-tert-butylbenzyl)-1-(pyridine-2-yl)-N-(pyridine-2-ylmethyl)methanamine
• CAS: 1191437-58-7
• 化学式: C₂₃H₂₆BrN₃
• 分子量: 424.384
• InChiKey: ROHJBEDRUUOLOH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.74
• 重原子数：
  27.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  29.02
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  N-(2-bromo-4-tert-butylbenzyl)-1-(pyridine-2-yl)-N-(pyridine-2-ylmethyl)methanamine 、 iron(II) bromide 以 四氢呋喃 为溶剂， 以97%的产率得到(κ-N,N(py)2-N-(2-bromo-4-tert-butylbenzyl)-1-(pyridine-2-yl)-N-(pyridine-2-ylmethyl)methanamine)FeBr2
  参考文献：
  名称：

  Aryl-Containing Chelates and Amine Debenzylation to Afford 1,3-Di-2-pyridyl-2-azaallyl (smif): Structures of {κ-C,N,N^py₂-(2-pyridylmethyl)₂N(CH₂(4-^tBu-phenyl-2-yl))}FeBr and (smif)CrN(TMS)₂

  摘要：

  Aryl-bromide ligand precursors have been prepared with the potential to afford tetradentate chelates (2-pyridylmethyl)(3-x)N(CH2-2-Aryl)(x)(x = 1, 2) containing metal-aryl linkages that promise to impart stronger fields about first row transition metals. Oxidative addition to Ni(COD)(2) afforded two diamagnetic Ni(II) complexes, (kappa-C,N,N-py-(2-pyridylmethyl)N(CH2(4-Bu-t-phenyl-2-yl))(CH2(4-Bu-t-phenyl-2-Br))}NiBr (1-Ni) and {(kappa-C,N,N-2(py)-(2-pyridylmethyl)(2)N(CH2(4-Bu-t-phenyl-2-yl))}NiBr (2-Ni) in 96% and 67% yield, respectively. Extending these synthetic efforts to iron provided {kappa-C,N,N-2(py)-(2-pyridylmethyl)(2)N(CH2(4-Bu-t-phenyl-2-yl))}FeBr (2-Fe, X-ray) in 91% yield via reduction of an adduct, {kappa-N,N-2(py)-(2-pyridylmethyl)(2)N(CH2(4-Bu-t-phenyl-2-Br))}FeBr2 (3-Fe). 5-Coordinate 2-Fe possessed a pseudo-tbp structure, and SQUID magnetometry showed it to be S = 2 with significant zero field splitting (ZFS). 2Fe was initially prepared via oxidative addition to Fe{N(TMS)(2))(2)(THF) upon disproportionation to "Fe(0)" and 2 Fe{N(TMS)(2)}(3), but when this approach was attempted with Cr{N(TMS)(2)}(2)(THF)(2), the azaallyl complex {kappa-N,N-2(py)-1,3-dipyridyl-2-azaallyl}CrN(TMS)(2) ((smif)CrN(TMS)(2), 4-Cr, X-ray), formed instead (>50%) via amine debenzylation. An alternative route consisting of addition of 1,3-di-2-pyridyl-2-azapropene to Cr{N(TMS)(2)}(2)(THF)(2) afforded 4-Cr in 74% yield. Pseudo-square planar 4-Cr was also S = 2 (SQUID) with marked ZFS. The dipyridylazaallyl ligand "smif" imparts a remarkable optical density to 4-Cr via intraligand bands at 675 nm (epsilon similar to 15 000 M(-1)cm(-1)) and 396 nm (epsilon similar to 27 000 M(-1)cm(-1)). The effective fields of the chelate complexes are discussed, and a comparison of smif to isoelectronic NHC ligands is given.

  DOI：

  10.1021/ic901329z