MeNH=BCy2 | 1347747-76-5

• 英文名称: MeNH=BCy2
• CAS: 1347747-76-5
• 化学式: C₁₃H₂₆BN
• 分子量: 207.167
• InChiKey: WXTPUKRVXDQXKL-UHFFFAOYSA-N

物化性质

• 沸点：
  293.9±23.0 °C(Predicted)
• 密度：
  0.87±0.1 g/cm3(Predicted)

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

• 作为产物：
  描述：

  MeNH2-BH2-NHMe-BH3 以 四氢呋喃 为溶剂， 反应 18.0h， 生成 甲胺硼烷 、 MeNH=BCy2
  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

文献信息

• Mechanistic Studies of the Dehydrocoupling and Dehydropolymerization of Amine–Boranes Using a [Rh(Xantphos)]⁺ Catalyst
  作者：Heather C. Johnson、Erin M. Leitao、George R. Whittell、Ian Manners、Guy C. Lloyd-Jones、Andrew S. Weller

  DOI：10.1021/ja503335g

  日期：2014.6.25

  approximation) operate during catalysis. B-N bond formation (with H3B·NMeH2) or elimination of amino-borane (with H3B·NMe2H) follows, in which N-H activation is proposed to be turnover limiting (KIE = 2.1 ± 0.2), with suggested mechanisms that only differ in that B-N bond formation (and the resulting propagation of a polymer chain) is favored for H3B·NMeH2 but not H3B·NMe2H. Importantly, for the dehydropolymerization

  使用 [Rh(Xantphos)](+) 片段对 H3B·NMe2H 的脱氢偶联和 H3B·NMeH2 的脱氢聚合进行了详细的催化、化学计量和机理研究。在 0.2 mol% 催化剂负载下，脱氢偶联分别产生二聚体 [H2B-NMe2]2 和聚（甲基氨基硼烷）（M(n) = 22,700 g mol(-1)，PDI = 2.1）。获得的化学计量和催化动力学数据表明，两种底物的作用机制相似，其中一个关键特征是产生活性催化剂的诱导期，建议是 Rh-酰胺基硼烷，它可逆地结合额外的胺-硼烷，从而饱和动力学（Michaelis-Menten 型稳态近似）在催化过程中起作用。BN 键形成（使用 H3B·NMeH2）或消除氨基硼烷（使用 H3B·NMe2H）如下，其中NH活化被认为是周转限制（KIE = 2.1±0.2），所建议的机制仅在于BN键的形成（以及由此产生的聚合物链的传播）有利于H3B·NMeH2而不是H3B·NMe2H
• Mechanisms of the Thermal and Catalytic Redistributions, Oligomerizations, and Polymerizations of Linear Diborazanes
  作者：Alasdair P. M. Robertson、Erin M. Leitao、Titel Jurca、Mairi F. Haddow、Holger Helten、Guy C. Lloyd-Jones、Ian Manners

  DOI：10.1021/ja404247r

  日期：2013.8.28

  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.