[Pb(tert-butoxide)(CH(C(Me)N(2,6-iPr2C6H3))2)] | 1187772-02-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [Pb(tert-butoxide)(CH(C(Me)N(2,6-iPr2C6H3))2)]
• CAS: 1187772-02-6
• 化学式: C₃₃H₅₀N₂OPb
• 分子量: 697.973
• InChiKey: UFFQFYVXWJJGPG-VCGBEGQOSA-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：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  二氧化碳 、 [Pb(tert-butoxide)(CH(C(Me)N(2,6-iPr2C6H3))2)] 以 氘代甲苯 为溶剂， 生成 [Pb(tert-butylcarbonate)(CH(C(Me)N(2,6-iPr2C6H3))2)]
  参考文献：
  名称：

  Carbon Dioxide Activation by “Non-nucleophilic” Lead Alkoxides

  摘要：

  A series of terminal lead alkoxides have been synthesized utilizing the bulky beta-diketiminate ligand [{N(2,6-(Pr2C6H3)-Pr-i)-C(Me)}(2)CH](-) (BDI). The nucleophilicities of these alkoxides have been examined, and unexpected trends were observed. For instance, (BDI)PbOR reacts with methyl iodide only under forcing conditions yet reacts readily, but reversibly, with carbon dioxide. The degree of reversibility is strongly dependent upon minor changes in the R group. For instance, when R = isopropyl, the reversibility is only observed when the resulting alkyl carbonate is treated with other heterocumulenes; however, when R = tert-butyl, the reversibility is apparent upon any application of reduced pressure to the corresponding alkyl carbonate. The differences in the reversibility of carbon dioxide insertion are attributed to the ground-state energy differences of lead alkoxides. The mechanism of carbon dioxide insertion is discussed.

  DOI：

  10.1021/ic900134f
• 作为产物：
  描述：

  [Pb(tert-butylcarbonate)(CH(C(Me)N(2,6-iPr2C6H3))2)] 以 not given 为溶剂， 生成 [Pb(tert-butoxide)(CH(C(Me)N(2,6-iPr2C6H3))2)]
  参考文献：
  名称：

  Carbon Dioxide Activation by “Non-nucleophilic” Lead Alkoxides

  摘要：

  A series of terminal lead alkoxides have been synthesized utilizing the bulky beta-diketiminate ligand [{N(2,6-(Pr2C6H3)-Pr-i)-C(Me)}(2)CH](-) (BDI). The nucleophilicities of these alkoxides have been examined, and unexpected trends were observed. For instance, (BDI)PbOR reacts with methyl iodide only under forcing conditions yet reacts readily, but reversibly, with carbon dioxide. The degree of reversibility is strongly dependent upon minor changes in the R group. For instance, when R = isopropyl, the reversibility is only observed when the resulting alkyl carbonate is treated with other heterocumulenes; however, when R = tert-butyl, the reversibility is apparent upon any application of reduced pressure to the corresponding alkyl carbonate. The differences in the reversibility of carbon dioxide insertion are attributed to the ground-state energy differences of lead alkoxides. The mechanism of carbon dioxide insertion is discussed.

  DOI：

  10.1021/ic900134f

文献信息

• Lead and tin β-diketiminato amido/anilido complexes: competitive nucleophilic reactivity at the β-diketiminato γ-carbon
  作者：Lisa A.-M. Harris、Eric C. Y. Tam、Martyn P. Coles、J. Robin Fulton

  DOI：10.1039/c4dt01714e

  日期：——

  The β-diketiminatolead(II)-amido and -anilido complexes, [(BDI)Pb(NRR′)] (BDI = [N(2,6-iPr2C6H3)C(Me)}2CH]; NRR′ = NH(2,6-iPr2C6H3), N(iPr)2), react at the amido/anilido nitrogen atom with simple saturated electrophiles such as methyltriflate. Addition of unsaturated electrophiles to these complexes either results in the formation of a complex mixture of products, or in the case of phenylisocyanate, reaction at the γ-carbon of the β-diketiminato ligand to form a complex that is the net result of a nucleophilic attack by the γ-carbon atom of the β-diketiminato ligand at the electrophilic carbon centre of phenylisocyanate. As this reactivity contrasts with that of β-diketiminatolead(II) alkoxo complexes as well as β-diketiminatotin(II) alkoxo complexes, we examined the reactivity between phenylisocyanate and the isostructural β-diketiminatotin(II)-amido and -anilido complexes. Reactivity at the γ-carbon was also observed in these systems. Density functional calculations were performed to help understand the differences in reactivity.

  β-二酮亚胺铅 (II)-amido 和 -anilido 配合物，[(BDI)Pb(NRRâ²)] (BDI = [N(2,6-iPr2C6H3)C(Me)}2CH];NRRâ² = NH(2,6-iPr2C6H3), N(iPr)2) 在酰胺基/苯胺基氮原子上与简单的饱和亲电子试剂（例如三氟甲磺酸甲酯）发生反应。将不饱和亲电子试剂添加到这些配合物中，要么导致形成复杂的产物混合物，要么在异氰酸苯酯的情况下，在 β-diketiminato 配体的 γ-碳上发生反应，形成配合物，这是亲核反应的最终结果在异氰酸苯酯的亲电碳中心受到β-二酮基配体的γ-碳原子的攻击。由于这种反应性与 β-diketiminatolead(II) 烷氧基络合物以及 β-diketiminatotin(II) 烷氧基络合物的反应性相反，我们检查了异氰酸苯酯和同结构 β-diketiminatotin(II)-amido 和 -anilido 络合物之间的反应性。在这些系统中还观察到γ-碳的反应性。进行密度泛函计算以帮助理解反应性的差异。