bromo(2,6-bis[(di-tert-butylphosphino)methyl]pyridine)copper(I) | 1028736-77-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: bromo(2,6-bis[(di-tert-butylphosphino)methyl]pyridine)copper(I)
• 英文别名: [CuBr(2,6-di(tert-butylphosphinomethyl)pyridine)]；[(2,6-((t-Bu)2PCH2)2C5H3N)CuBr]；copper(1+);ditert-butyl-[[6-(ditert-butylphosphanylmethyl)pyridin-2-yl]methyl]phosphane;bromide
• CAS: 1028736-77-7
• 化学式: C₂₃H₄₃BrCuNP₂
• 分子量: 538.999
• InChiKey: QTOYIGRRFHYJLK-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.24
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bromo(2,6-bis[(di-tert-butylphosphino)methyl]pyridine)copper(I) 在 NaN(SiMe₃)2 or KO-t-Bu 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成
  参考文献：
  名称：

  Cu^I Complexes with a Noninnocent PNP Ligand: Selective Dearomatization and Electrophilic Addition Reactivity

  摘要：

  The neutral, T-shaped complex Cu-I((PN-PtBu)) (2), featuring a dearomatized 2,6-bis(diphosphino)pyridine (PNP)-pincer ligand, is shown to interact rapidly with electrophiles. This has enabled the synthesis of acetato complex 3. Furthermore, C-C bond formation onto the deprotonated methylene-bridgehead carbon is observed with MeOTf as the electrophile. This represents the first case of selective modification of the lutidine-based backbone of such noninnocent PNP ligands. Theoretical calculations support the formation of monomeric complex 2 and indicate the high reactivity of the methylene fragment in this Cu-I complex.

  DOI：

  10.1021/ic901032c
• 作为产物：
  描述：

  2,6-双(二叔丁基膦基甲基)吡啶 、 溴化亚铜二甲硫醚 以 乙醚 为溶剂， 生成 bromo(2,6-bis[(di-tert-butylphosphino)methyl]pyridine)copper(I)
  参考文献：
  名称：

  T-Shaped Cationic Cu^I Complexes with Hemilabile PNP-Type Ligands

  摘要：

  The versatile coordination behavior of the PNP ligands 1A (2,6-bis[(di-tert-butylphosphino)methyl]pyridine) and 1B (2,6-bis[(diphenylphosphino)methyl]pyridine) to Cu-I is described, whereby a hemilabile interaction of the pyridine N-donor atom to the copper center resulted in a rare T-shaped complex with 1A, while with 1B also a tetracoordinated species could be isolated. Theoretical calculations support the weak interaction of the pyridine N donor in 1A with the Cu center.

  DOI：

  10.1021/ic800298a

文献信息

• CuI click catalysis with cooperative noninnocent pyridylphosphine ligands
  作者：Sandra Y. de Boer、Yann Gloaguen、Martin Lutz、Jarl Ivar van der Vlugt

  DOI：10.1016/j.ica.2011.10.037

  日期：2012.1

  We describe the synthesis and characterization of compound L1H, 2-di(tert-butyl)phosphinomethyl-6-methylpyridine, and the first dimeric CuI complex 3 with this novel bidentate NPtBu ligand. We also demonstrate for the first time that this ligand scaffold exhibits noninnocent reactivity through dearomatization behavior, similar to its well-studied tridentate analog L2H, 2,6-bis((di-tert-butylphosphino)methyl)pyridine

  我们描述了化合物L1H，2-二（叔丁基）膦基甲基-6-甲基吡啶和第一个具有这种新型双齿NPtBu配体的二聚CuI配合物3的合成和表征。我们还首次证明了该配体支架通过脱芳香化行为表现出非清白的反应性，类似于对其充分研究的三齿类似物L2H，2,6-双（（二叔丁基膦基）甲基）吡啶PNPtBu。据报道[Cu（CCPh）（L2H）] 2的分子结构，这是晶体学表征的乙炔铜二聚体的罕见情况。我们还证明，与配体L1H或L2H或其脱芳构的对应物形成的铜（I）配合物可充当叠氮化物和乙炔的[2 + 3]极性环加成反应的活性，协同催化剂。