μ-(CH3)2NB2H5*NH2CH3 | 21793-60-2

• 英文名称: μ-(CH3)2NB2H5*NH2CH3
• CAS: 21793-60-2
• 化学式: C₃H₁₆B₂N₂
• 分子量: 101.795
• InChiKey: NWQJFHDQHFJMMZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  μ-(CH3)N-B2H5*N(CH3)3 、 甲胺 以 四氢呋喃 为溶剂， 反应 16.0h， 以0.12 g的产率得到μ-(CH3)2NB2H5*NH2CH3
  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

文献信息

• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: B: B-Verb.10, 2.2, page 24 - 27
  作者：

  DOI：——

  日期：——
• Studies of Boron-Nitrogen Compounds. VII.¹ Synthesis and Properties of 1,3-Methyl-Substituted Diborazanes²
  作者：George A. Hahn、Riley. Schaeffer

  DOI：10.1021/ja01062a010

  日期：1964.4