tris((4,4-dimethyl-2-oxazolinyl)phenylborate)ZnEt | 1392266-03-3

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: tris((4,4-dimethyl-2-oxazolinyl)phenylborate)ZnEt
• 英文别名: tris(4,4-dimethyl-2-oxazolinyl)phenylborato(ethyl)zinc
• CAS: 1392266-03-3
• 化学式: C₂₃H₃₄BN₃O₃Zn
• 分子量: 476.742
• InChiKey: ORUBPRFBZPKGSR-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：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 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：

  tris((4,4-dimethyl-2-oxazolinyl)phenylborate)ZnEt 在 P(C₆H₅)3 or P(C₆H₄CH₄)3 or P(CH₃)3 or PH₂C₆H₅ 作用下， 以 癸烷 、 氘代甲苯 、 苯 为溶剂， 生成 tris(4,4-dimethyl-2-oxazolinyl)phenylborato(tert-butyloxy)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：

  H[tris((4,4-dimethyl-2-oxazolinyl)phenylborate)] 、 diethylzinc 以 苯 为溶剂， 以89.3%的产率得到tris((4,4-dimethyl-2-oxazolinyl)phenylborate)ZnEt
  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

文献信息

• Divergent reaction pathways of tris(oxazolinyl)borato zinc and magnesium silyl compounds
  作者：Debabrata Mukherjee、Nicole L. Lampland、KaKing Yan、James F. Dunne、Arkady Ellern、Aaron D. Sadow

  DOI：10.1039/c2cc36953b

  日期：——

  Synthesis and reactivity of monomeric magnesium and zinc silyl compounds To(M)M-Si(SiHMe2)3 and To(M)M-Si(SiMe3)3 are described (To(M) = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The magnesium compounds react slowly with water and air, while the zinc compounds are inert. With CO2, To(M)Mg-Si(SiHMe2)3 provides To(M)MgO2CSi(SiHMe2)3 through CO2 insertion, whereas To(M)Zn-Si(SiHMe2)3 affords To(M)ZnOCHO

  描述了单体镁和锌甲硅烷基化合物To（M）M-Si（SiHMe2）3和To（M）M-Si（SiMe3）3的合成和反应性（To（M）= tris（4,4-dimethyldimethyl-2 -恶唑啉基）苯基硼酸酯）。镁化合物与水和空气缓慢反应，而锌化合物是惰性的。对于CO2，To（M）Mg-Si（SiHMe2）3通过插入 提供To（M）MgO2CSi（SiHMe2）3，而To（M）Zn-Si（SiHMe2）3提供To（M）ZnOCHO。