tris(4,4-dimethyl-2-oxazolinyl)phenylborato(tert-butyl)zinc | 1392266-06-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: tris(4,4-dimethyl-2-oxazolinyl)phenylborato(tert-butyl)zinc
• 英文别名: zinc;2-methylpropane;tris(4,4-dimethyl-5H-1,3-oxazol-2-yl)-phenylboranuide
• CAS: 1392266-06-6
• 化学式: C₂₅H₃₈BN₃O₃Zn
• 分子量: 504.796
• InChiKey: QQFRFMKLQIRYFG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  33
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  64.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  tris(4,4-dimethyl-2-oxazolinyl)phenylborato(tert-butyl)zinc 以 氘代苯 、 苯 为溶剂， 生成 bis(κ2-tris(4,4-dimethyl-2-oxazolinyl)phenylborato)zinc
  参考文献：
  名称：

  Remarkably Robust Monomeric Alkylperoxyzinc Compounds from Tris(oxazolinyl)boratozinc Alkyls and O₂

  摘要：

  Metal alkylperoxides are remarkable, highly effective, yet often thermally unstable, oxidants that may react through a number of possible pathways including O-O homolytic cleavage, M-O homolytic cleavage, nucleophilic O-atom transfer, and electrophilic O-atom transfer. Here we describe a series of zinc alkyl compounds of the type To(M)ZnR (To(M) = tris(4,4-dimethyl-2-oxazolinyl)phenylborate; R = Et, n-C3H7, i-C3H7, t-Bu) that react with O-2 at 25 degrees C to form isolable monomeric alkylperoxides To(M)ZnOOR in quantitative yield. The series of zinc alkylperoxides is crystallographically characterized, and the structures show systematic variations in the Zn-O-O angle and O-O distances. The observed rate law for the reaction of To(M)ZnEt (2) and O-2 is consistent with a radical chain mechanism, where the rate-limiting S(H)2 step involves the interaction of (OOR)-O-center dot and To(M)ZnR. In contrast, To(M)ZnH and To(M)ZnMe are unchanged even to 120 degrees C under 100 psi of O-2 and in the presence of active radical chains (e.g., (OOEt)-O-center dot). This class of zinc alkylperoxides is unusually thermally robust, in that the compounds are unchanged after heating at 120 degrees C in solution for several days. Yet, these compounds are reactive as oxidants with phosphines. Additionally, an unusual alkylperoxy group transfer to organosilanes affords To(M)ZnH and ROOSiR3'.

  DOI：

  10.1021/ja303440n
• 作为产物：
  描述：

  二(2-甲基-2-丙基)锌 、 thallium tris(4,4-dimethyl-2-oxazolinyl)phenylborate 以 乙醚 为溶剂， 生成 tris(4,4-dimethyl-2-oxazolinyl)phenylborato(tert-butyl)zinc
  参考文献：
  名称：

  Remarkably Robust Monomeric Alkylperoxyzinc Compounds from Tris(oxazolinyl)boratozinc Alkyls and O₂

  摘要：

  Metal alkylperoxides are remarkable, highly effective, yet often thermally unstable, oxidants that may react through a number of possible pathways including O-O homolytic cleavage, M-O homolytic cleavage, nucleophilic O-atom transfer, and electrophilic O-atom transfer. Here we describe a series of zinc alkyl compounds of the type To(M)ZnR (To(M) = tris(4,4-dimethyl-2-oxazolinyl)phenylborate; R = Et, n-C3H7, i-C3H7, t-Bu) that react with O-2 at 25 degrees C to form isolable monomeric alkylperoxides To(M)ZnOOR in quantitative yield. The series of zinc alkylperoxides is crystallographically characterized, and the structures show systematic variations in the Zn-O-O angle and O-O distances. The observed rate law for the reaction of To(M)ZnEt (2) and O-2 is consistent with a radical chain mechanism, where the rate-limiting S(H)2 step involves the interaction of (OOR)-O-center dot and To(M)ZnR. In contrast, To(M)ZnH and To(M)ZnMe are unchanged even to 120 degrees C under 100 psi of O-2 and in the presence of active radical chains (e.g., (OOEt)-O-center dot). This class of zinc alkylperoxides is unusually thermally robust, in that the compounds are unchanged after heating at 120 degrees C in solution for several days. Yet, these compounds are reactive as oxidants with phosphines. Additionally, an unusual alkylperoxy group transfer to organosilanes affords To(M)ZnH and ROOSiR3'.

  DOI：

  10.1021/ja303440n