tris(4,4-dimethyl-2-oxazolinyl)phenylborato(n-propylperoxy)zinc | 1392266-10-2

• 分子结构分类: 有机化合物
• 英文名称: tris(4,4-dimethyl-2-oxazolinyl)phenylborato(n-propylperoxy)zinc
• 英文别名: ToMZnOOnPr；zinc;1-oxidooxypropane;tris(4,4-dimethyl-5H-1,3-oxazol-2-yl)-phenylboranuide
• CAS: 1392266-10-2
• 化学式: C₂₄H₃₆BN₃O₅Zn
• 分子量: 522.768
• InChiKey: QQNSIABPAXEJFL-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.27
• 重原子数：
  34
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  97.1
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  tris(4,4-dimethyl-2-oxazolinyl)phenylborato(n-propylperoxy)zinc 在 P(C₆H₅)3 or P(C₆H₄CH₄)3 or P(CH₃)3 or PH₂C₆H₅ 作用下， 以 氘代甲苯 为溶剂， 生成 tris(4,4-dimethyl-2-oxazolinyl)phenylborato(n-propyloxy)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：

  thallium tris(4,4-dimethyl-2-oxazolinyl)phenylborate 以 乙醚 、 苯 为溶剂， 生成 tris(4,4-dimethyl-2-oxazolinyl)phenylborato(n-propylperoxy)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