Uncatalyzed Formation of Polyaminoboranes from Diisopropylaminoborane and Primary Amines: a Kinetically Controlled Polymerization Reaction,Advanced Synthesis & Catalysis

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Uncatalyzed Formation of Polyaminoboranes from Diisopropylaminoborane and Primary Amines: a Kinetically Controlled Polymerization Reaction
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2020-12-21 , DOI: 10.1002/adsc.202001458
Marc Devillard ₁ , Carlos Antonio De Albuquerque Pinheiro ₁ , Elsa Caytan ₁ , Claire Roiland ₁ , Chiara Dinoi ₂ , Iker Del Rosal ₂ , Gilles Alcaraz ₁

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Recently, we disclosed the uncatalyzed formation of polyaminoboranes (PABs) from monomeric diisopropylaminoborane (ⁱPr₂N−BH₂) and primary amines (RNH₂). Their structure is studied through a detailed multinuclear NMR study and their full spectroscopic characterization is presented revealing that N‐alkyl substituted PABs exhibit magnetically non‐equivalent methylenic protons in the close vicinity of the BN‐backbone. We also performed an in‐depth theoretical study of this global chemical process. The mechanism is fully apprehended and the strong influence of the temperature on the outcome of the reaction is unveiled. DFT‐calculations clearly show that the formation of the polyaminoboranes (RNH−BH₂)_n results from a kinetically controlled step‐growth polymerization reaction that can be globally viewed as a head‐to‐tail association process of the in situ generated transient monomeric monoalkylamino‐borane [RNH−BH₂].

中文翻译：

由二异丙基氨基硼烷和伯胺未催化形成的聚氨基硼烷：动力学控制的聚合反应

最近，我们公开了由单体二异丙基氨基硼烷（ⁱ Pr ₂ N-BH ₂）和伯胺（RNH ₂）催化形成的聚氨基硼烷（PAB ）。通过详细的多核NMR研究对它们的结构进行了研究，并给出了其完整的光谱特征，表明N烷基取代的PAB在BN骨干附近表现出磁性不等价的亚甲基质子。我们还对该全球化学过程进行了深入的理论研究。充分理解了机理，并揭示了温度对反应结果的强烈影响。DFT计算清楚地表明，聚氨基硼烷（RNH-BH ₂）的形成_n是由动力学控制的逐步增长的聚合反应产生的，该反应可以整体上视为原位生成的瞬态单体单烷基氨基硼烷[RNH-BH ₂ ]的头尾结合过程。

更新日期：2020-12-21

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