bis(methylamino)borane | 14755-20-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: bis(methylamino)borane
• 英文别名: HB(NHMe)2；N-(methylaminoboranyl)methanamine
• CAS: 14755-20-5
• 化学式: C₂H₉BN₂
• 分子量: 71.9179
• InChiKey: VQAGDPYFJINRMC-UHFFFAOYSA-N

物化性质

• 沸点：
  54.2±23.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.31
• 重原子数：
  5.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  24.06
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  甲胺 在 (t-C4H9SBH2)3 作用下， 以 四氢呋喃 为溶剂， 生成 bis(methylamino)borane 、 甲胺硼烷
  参考文献：
  名称：

  Synthesis and the Thermal and Catalytic Dehydrogenation Reactions of Amine-Thioboranes

  摘要：

  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.

  DOI：

  10.1021/ic3008188

文献信息

• Dehydrocoupling Reactions of Borane−Secondary and −Primary Amine Adducts Catalyzed by Group-6 Carbonyl Complexes: Formation of Aminoboranes and Borazines
  作者：Yasuro Kawano、Mikio Uruichi、Mamoru Shimoi、Seitaro Taki、Takayuki Kawaguchi、Taeko Kakizawa、Hiroshi Ogino

  DOI：10.1021/ja904918u

  日期：2009.10.21

  solution of BH(3).NHR(2) (1a: R = Me, 1b: R = 1/2C(4)H(8), 1c: R = 1/2C(5)H(10), 1f: R = Et) containing a catalytic amount of a group-6 metal carbonyl complex, [M(CO)(6)] (M = Cr, Mo, W), led to dehydrogenative B-N covalent bond formation to produce aminoborane dimers, [BH(2)NR(2)](2) (2a-c, f), in high yield. During these reactions a borane sigma complex, [M(CO)(5)(eta(1)-BH(3).NHR(2))] (3), was detected

  BH(3).NHR(2) 溶液的光辐照 (1a: R = Me, 1b: R = 1/2C(4)H(8), 1c: R = 1/2C(5)H(10) , 1f: R = Et) 含有催化量的第 6 族金属羰基络合物 [M(CO)(6)] (M = Cr, Mo, W)，导致脱氢 BN 共价键形成以产生氨基硼烷二聚体, [BH(2)NR(2)](2) (2a-c, f)，产量高。在这些反应中硼烷西格玛复合物，[M(CO)(5)(eta(1)-BH(3).NHR(2))] (3)，被核磁共振波谱检测到。体积较大的胺硼烷、BH(3).NH(i)Pr(2) (1d) 和 BH(3).NHCy(2) (1e, Cy = cyclo-C(6)H(11)) 的类似催化脱氢，得到单体产物 BH(2) 水平线 NR(2) (4d, e)。通过DFT计算研究了脱氢偶联的反应机理。在计算研究的基础上，我们建议催
• Rhodium(I) PNN Pincer Complexes with Proton‐responsive Ligands: Synthesis, Characterisation, and Catalytic Dehydrocoupling of Amine Boranes
  作者：Mirko Rippke、Hans‐Joachim Drexler、Torsten Beweries

  DOI：10.1002/ejic.202300463

  日期：2023.12

  Pyrazole-based PNN(H) RhI complexes are active catalysts for the dehydrocoupling of amine boranes to produce cyclic oligomers. Efficient dehydrohalogenation of the Rh chloride precursor complex and ligand deprotonation are essential for the realization of high catalytic activity.

  吡唑基 PNN(H) Rh I配合物是胺硼烷脱氢偶联生成环状低聚物的活性催化剂。氯化铑前体络合物的有效脱卤化氢和配体去质子化对于实现高催化活性至关重要。
• Ambient Temperature Carbene-Mediated Depolymerization: Stoichiometric and Catalytic Reactions of <i>N</i>-Heterocyclic- and Cyclic(Alkyl)Amino Carbenes with Poly(<i>N</i>-Methylaminoborane) [MeNH–BH₂]_<i>n</i>
  作者：Nicola L. Oldroyd、Saurabh S. Chitnis、Etienne A. LaPierre、Vincent T. Annibale、Henry T. G. Walsgrove、Derek P. Gates、Ian Manners

  DOI：10.1021/jacs.2c10931

  日期：2022.12.21