nBuNH2*BH3 | 24482-62-0

• 英文名称: nBuNH2*BH3
• 英文别名: n-butylamine borane complex；n-butylamine-borane；butylamine-borane；(n-C4H9)H2N*BH3
• CAS: 24482-62-0
• 化学式: C₄H₁₄BN
• 分子量: 86.9729
• InChiKey: LBXXQMQMMGAVEX-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：

  nBuNH2*BH3 在 [(κ³-C₆H₃-1,3-[OP^tBu₂]₂)Ir(H)_2] 作用下， 以 四氢呋喃 为溶剂， 以82%的产率得到poly(N-butylaminoborane)
  参考文献：
  名称：

  铱催化的伯胺-硼烷加合物的脱氢偶联：通往高分子量聚氨基硼烷，聚烯烃硼氮类似物的途径。

  摘要：

  DOI：

  10.1002/anie.200801197
• 作为产物：
  描述：

  {(n-C4H9NH2)2BH2}{SC2H5} 以33%的产率得到nBuNH2*BH3
  参考文献：
  名称：

  Shchegoleva, T. A.; Shashkova, E. M.; Mikhailov, B. M., Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1969, p. 317 - 320

  摘要：

  DOI：

文献信息

• Efficient reductions of dimethylhydrazones using preformed primary amine boranes
  作者：Christian Frabitore、Jérome Lépeule、Bradley Towey、Tom Livinghouse、William C. Robinson

  DOI：10.1080/00397911.2021.2008449

  日期：2022.1.17

  Abstract A convenient method for the reduction of N,N-dimethylhydrazones using amine borane complexes generated in situ is described. It was found that primary amine borane complexes performed exceedingly well at reducing N,N-dimethylhydrazones in as little as 1.1 equivalents, furnishing the corresponding air-sensitive hydrazine products in excellent yields.

  摘要 描述了一种使用原位生成的胺硼烷络合物还原 N,N-二甲基腙的简便方法。研究发现，伯胺硼烷络合物在还原 N,N-二甲基腙方面表现非常出色，只需 1.1 当量，即可以优异的收率提供相应的空气敏感肼产品。
• Synthesis, characterisation, and dehydrocoupling ability of zirconium complexes bearing hindered bis(amido)silyl ligands
  作者：Paul A. Lummis、Robert McDonald、Michael J. Ferguson、Eric Rivard

  DOI：10.1039/c5dt00306g

  日期：——

  Herein we detail the synthesis and characterisation of a series of zirconium compounds featuring the bis(amido)silyl ligand [iPr2Si(NDipp)2]2− (Dipp = 2,6-diisopropylphenyl). The functionalisation of bis(amido)silyl zirconium halide complexes with a variety of nucleophiles, such as LiNMe2, LiBH4 and MeLi, was explored and the resulting products showed a propensity to form anionic zirconate salts when

  本文中，我们详细介绍了一系列具有双（酰胺基）甲硅烷基配体[ i Pr 2 Si（NDipp）2 ] 2-（Dipp = 2,6-二异丙基苯基）的锆化合物的合成和表征。探索了双（酰胺基）甲硅烷基卤化锆配合物与多种亲核试剂如LiNMe 2，LiBH 4和MeLi的功能化，并且当在THF中进行合成时，所得产物显示出形成阴离子锆酸盐的倾向。锆酸盐产品之一[ i Pr 2 Si（NDipp）2 ] Zr（NMe 2）2 ·ClLi（THF）3具有在室温下在芳族溶剂中催化伯胺和仲胺硼烷的脱氢偶联的能力。
• Coordination Chemistry of Borane in Solution: Application to a STING Agonist
  作者：Alexander Zhdanko、Boris A. Worp、Sébastien Lemaire

  DOI：10.1002/ejoc.202200130

  日期：2022.4.5

  Comparing nitrogen bases having equal steric properties, a linear correlation of BH 3 binding affinity vs. Brønsted acidity was found. This correlation can be used to quickly estimate the BH 3 binding affinity of a substrate if p K a is known. Kinetic studies suggest the ligand exchange to occur as a bimolecular S N 2 reaction unless other nucleophilic species were present in the reaction mixture.

  确定了硼烷配合物与溶液中各种氧、硫、氮和磷亲核试剂的配体交换反应的平衡常数，并建立了一个跨越 12 个数量级的结合亲和力尺度。虽然 K eq 对溶剂的依赖性极小，但配体交换速率差异很大。在 THF 和 CDCl 3 中分别观察到最快和最慢的速率。此外，根据起始复合物的稳定性，配体交换率在非常宽的范围内不同。发现 BH 3 的结合对空间因子比质子化更敏感。比较具有相同空间特性的氮碱基，发现 BH 3 结合亲和力与布朗斯台德酸度的线性相关。如果 p K a 已知，则该相关性可用于快速估计底物的 BH 3 结合亲和力。动力学研究表明，除非反应混合物中存在其他亲核物质，否则配体交换会作为双分子 SN 2 反应发生。
• Uncatalyzed Formation of Polyaminoboranes from Diisopropylaminoborane and Primary Amines: a Kinetically Controlled Polymerization Reaction
  作者：Marc Devillard、Carlos Antonio De Albuquerque Pinheiro、Elsa Caytan、Claire Roiland、Chiara Dinoi、Iker Del Rosal、Gilles Alcaraz

  DOI：10.1002/adsc.202001458

  日期：2021.4.27

  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

  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。
• Synthesis and the Thermal and Catalytic Dehydrogenation Reactions of Amine-Thioboranes
  作者：Alasdair P. M. Robertson、Mairi F. Haddow、Ian Manners

  DOI：10.1021/ic3008188

  日期：2012.8.6

  A series of trimethylamine-thioborane adducts, Me3N center dot BH2SR (R = tBu [2a], nBu [2b], iPr [2c], Ph [2d], C6F5 [2e]) have been prepared and characterized. Attempts to access secondary and primary amine adducts of thioboranes via amine-exchange reactions involving these species proved unsuccessful, with the thiolate moiety shown to be vulnerable to displacement by free amine. However, treatment of the arylthioboranes, [BH2-SPh](3) (9) and C6F5SBH2 center dot SMe2 (10) with Me2NH and iPr(2)NH successfully yielded the adducts Me2NH center dot BH2SR (R = Ph [11a], C6F5 [12a]) and iPr(2)NH center dot BH2SR (R = Ph [11b], C6F5 [12b]) in high yield. These adducts were also shown to be accessible via thermally induced hydrothiolation of the aminoboranes Me2N=BH2, derived from the cyclic dimer [Me2N-BH2](2) (13), and iPr(2)N=BH2 (14), respectively. Attempts to prepare the aliphatic thiolate substituted adducts R2NH center dot BH2SR' (R = Me, iPr; R' = tBu, nBu, iPr) via this method, however, proved unsuccessful, with the temperatures required to facilitate hydrothiolation also inducing thermal dehydrogenation of the amine-thioborane products to form aminothioboranes, R2N=BH(SR'). Thermal and catalytic dehydrogenation of the targeted amine-thioboranes, 11a/11b and 12a/12b were also investigated. Adducts 11b and 12b were cleanly dehydrogenated to yield iPr(2)N=BH(SPh) (22) and iPr(2)N=BH(SC6F5) (23), respectively, at 100 degrees C (18 h, toluene), with dehydrogenation also possible at 20 degrees C (42 h, toluene) with a 2 mol % loading of [Rh(mu-Cl)cod](2) in the case of the former species. Similar studies with adduct ha evidenced a competitive elimination of H-2 and HSPh upon thermolysis, and other complex reactivity under catalytic conditions, whereas the fluorinated analogue 12a was found to be resistant to dehydrogenation.