Me3N-BH2-NHMe-BH3 | 1349095-84-6

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: Me3N-BH2-NHMe-BH3
• 英文别名: [Boranuidyl(methyl)azaniumyl]-(trimethylazaniumyl)boranuide；[boranuidyl(methyl)azaniumyl]-(trimethylazaniumyl)boranuide
• CAS: 1349095-84-6
• 化学式: C₄H₁₈B₂N₂
• 分子量: 115.822
• InChiKey: DAPHPHBAADELRC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -3.51
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  4.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Me3N-BH2-NHMe-BH3 以 四氢呋喃 为溶剂， 反应 16.0h， 以53%的产率得到硼烷-三甲胺络合物
  参考文献：
  名称：

  Catalytic Redistribution and Polymerization of Diborazanes: Unexpected Observation of Metal-Free Hydrogen Transfer between Aminoboranes and Amine-Boranes

  摘要：

  Ir-catalyzed (20 degrees C) or thermal (70 degrees C) dehydrocoupling of the linear diborazane MeNH2-BH2-NHMe-BH3 led to the formation of poly- or oligoamino-boranes [MeNH-BH2](x) (x = 3 to > 1000) via an initial redistribution process that forms MeNH2 center dot BH3 and also transient MeNH=BH2, which exists in the predominantly metal-bound and free forms, respectively. Studies of analogous chemistry led to the discovery of metal-free hydrogenation of the B=N bond in the "model" aminoborane iPr(2)N=BH2 to give iPr(2)NH center dot BH3 upon treatment with the diborazane Me3N-BH2-NHMe-BH3 or amine-boranes RR'NH center dot BH3 (R, R' = H or Me).

  DOI：

  10.1021/ja208752w
• 作为产物：
  描述：

  BH2(μ-MeNH)(μ-H)BH2 、 三甲胺 以 甲苯 为溶剂， 反应 1.75h， 以89%的产率得到Me3N-BH2-NHMe-BH3
  参考文献：
  名称：

  Mechanisms of the Thermal and Catalytic Redistributions, Oligomerizations, and Polymerizations of Linear Diborazanes

  摘要：

  Linear diborazanes R3N-BH2-NR2-BH3 (R = alkyl or H) are often implicated as key intermediates in the dehydrocoupling/dehydrogenation of amine-boranes to form oligo-and polyaminoboranes. Here we report detailed studies of the reactivity of three related examples: Me3N-BH2-NMe2-BH3 (1), Me3N-BH2-NHMe-BH3 (2), and MeNH2-BH2-NHMe-BH3 (3). The mechanisms of the thermal and catalytic redistributions of 1 were investigated in depth using temporal-concentration studies, deuterium labeling, and DFT calculations. The results indicated that, although the products formed under both thermal and catalytic regimes are identical (Me3N center dot BH3 (8) and [Me2N-BH2](2) (9a)), the mechanisms of their formation differ significantly. The thermal pathway was found to involve the dissociation of the terminal amine to form [H2B(mu-H)(mu-NMe2)BH2] (5) and NMe3 as intermediates, with the former operating as a catalyst and accelerating the redistribution of 1, Intermediate 5 was then transformed to amine-borane 8 and the cyclic diborazane 9a by two different mechanisms. In contrast, under catalytic conditions (0.3-2 mol % IrH2POCOP (POCOP = kappa(3)-1,3-(OPtBu2)(2)C6H3)), 8 was found to inhibit the redistribution of 1 by coordination to the Ir-center. Furthermore, the catalytic pathway involved direct formation of 8 and Me2N=BH2 (9b), which spontaneously dimerizes to give 9a, with the absence of 5 and BH3 as intermediates. The mechanisms elucidated for 1 are also likely to be applicable to other diborazanes, for example, 2 and 3, for which detailed mechanistic studies are impaired by complex post-redistribution chemistry. This includes both metal-free and metal-mediated oligomerization of MeNH=BH2 (10) to form oligoaminoborane [MeNH-BH2](x) (11) or polyaminoborane [MeNH-BH2](n) (16) following the initial redistribution reaction.

  DOI：

  10.1021/ja404247r