potassium oxapentadienide | 131104-72-8

• 英文名称: potassium oxapentadienide
• CAS: 131104-72-8
• 化学式: C₄H₅O*K
• 分子量: 108.181
• InChiKey: VXRYYMGKEUGACT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Rh(μ-Cl)(PMe3)2]2 、 potassium oxapentadienide 以 四氢呋喃 为溶剂， 以68%的产率得到((1-3-η)-5-oxapentadienyl)bis(trimethylphosphine)rhodium
  参考文献：
  名称：

  氧杂戊二烯基-铑-膦化学1

  摘要：

  用氧杂戊二烯化钾处理[（PR 3）2 Rh（μ-Cl）] 2（R = Me或Et）导致产生（（1-3-n）-5-氧杂戊二烯基）Rh（PR 3）2（1，R = Me; 2，R = Et）为反式和顺式异构体的平衡混合物。同样，用2,4-二甲基恶戊二烯酸钾处理[（PR 3）2 Rh（μ-Cl）] 2（R = Me，Et）会生成（（1-3-n）-2,4-二甲基-5-氧杂戊二烯基）Rh（PR 3）2（3，R ＝ Me；4，R ＝ Et）。化合物3和4主要以反异构体的形式存在，但冷却后表现出两种旋转异构形式，镰刀形和U形旋转异构体。用另外1当量的PMe 3处理1会产生18e种（（1-3-n）-5-氧杂戊二烯基）Rh（PMe 3）3（5），在室温下稳定。相反，当用另外的1当量的PEt 3处理2时，在室温下无法通过NMR检测到反应。然而，在冷却至-70℃时，通过NMR观察到膦加合物（（1-3-n）-5-氧杂戊二烯基）Rh（PEt

  DOI：

  10.1021/om020429u

文献信息

• Bleeke, John R.; Haile, Tesfamichael; Chiang, Michael Y., Organometallics, 1991, vol. 10, # 1, p. 19 - 21
  作者：Bleeke, John R.、Haile, Tesfamichael、Chiang, Michael Y.

  DOI：——

  日期：——
• Bleeke, John R.; Haile, Tesfamichael; New, Pamela R., Organometallics, 1993, vol. 12, # 2, p. 517 - 528
  作者：Bleeke, John R.、Haile, Tesfamichael、New, Pamela R.、Chiang, Michael Y.

  DOI：——

  日期：——
• Synthesis, Structure, Spectroscopy, and Reactivity of Oxapentadienyl−Cobalt−Phosphine Complexes^,
  作者：John R. Bleeke、Bryn L. Lutes、Michael Lipschutz、Donastas Sakellariou-Thompson、John Seonghyun Lee、Nigam P. Rath

  DOI：10.1021/om100361a

  日期：2010.11.8

  The first examples of oxapentadienyl-cobalt complexes have been synthesized and structurally characterized. Treatment of (Cl)Co(PMe3)(3) with potassium oxapentadienide produces ((1,2,3-eta)-5-oxapentadienyl)Co(PMe3)(3) (1), while the reaction of (Cl)Co(PMe3)(3) with potassium 2,4-dimethyloxapentadienide generates ((1,2,3-eta)-2,4-dimethyl-5-oxapentadienyl)Co(PMe3)(3) (2). Both 1 and 2 undergo ligand substitution reactions when treated with excess carbon monoxide. Compound 1 reacts with 1 equiv of CO to produce ((1,2,3-eta)-5-oxapentadienyl)Co(PMe3)(2)(CO) (3), while 2 undergoes a double CO substitution to generate ((1,2,3-eta)-2,4-dimethyl-5-oxapentadienyl)Co(PMe3)(CO)(2) (4). Compound 3 can also be synthesized by reacting (Cl)Co(PMe3)(2)(CO)(2) with potassium oxapentadienide, but the analogous reaction involving potassium 2,4-dimethyloxapentadienide results in reduction of the cobalt starting material and production of the Co(0) dimer (CO)(PMe3)(2)Co(PMe)(2)Co(PMe3)(2)(Co) (5). Treatment of 1 with triflic acid (HO3SCF3) or methyl triflate (MeO3SCF3) results in electrophilic attack at oxygen and production of (eta(4)-butadienol)Co(PMe3)(3)+O3SCF3- (6) or (eta(4)-butadienyl methyl ether)Co(PMe3)3+O3SCF3- (7). Treatment of 2 with triflic acid or methyl triflate also results in electrophilic attack at oxygen; however, these products are unstable and rapidly lose their protonated or methylated ligands. The resulting Co(PMe3)4+O3SCF3-, generated in situ, reacts with excess carbon monoxide to produce Co(PMe3)(3)(CO)(2)+O3SCF3- (8). Compounds 1-8 have been characterized by single-crystal X-ray diffraction.