(methylamino)dihydroborane | 6601-31-6

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: (methylamino)dihydroborane
• 英文别名: methylamineborane；N-methylborazene；poly(N-methylaminoborane)；poly(methylaminoborane)；[(methylamide)B(hydride)2]n；N-boranylmethanamine
• CAS: 6601-31-6
• 化学式: CH₆BN
• 分子量: 42.8763
• InChiKey: JSOXCIMBEXFCPV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.25
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (methylamino)dihydroborane 在 碘 作用下， 以 四氢呋喃 为溶剂， 生成 dihydrobis(methylamine)borate triiodide
  参考文献：
  名称：

  Dihydrobis(methylamine)borate triiodide

  摘要：

  Both cation and anion in the title compound, C2H12BN2+.I-3(-), lie on a crystallographic mirror plane and are bound in the lattice by N-HcI(-) hydrogen bonds, forming layers. Methyl-H-borane-H dihydride [-C-H(delta(+))c(delta(-))H-B-] inter-actions between molecules crosslink adjacent layers, giving `sandwich' stacking along the a axis.

  DOI：

  10.1107/s010827010603335x
• 作为产物：
  描述：

  MeNH2-BH2-NHMe-BH3 在 [(κ³-C₆H₃-1,3-[OP^tBu₂]₂)Ir(H)_2] 作用下， 以 四氢呋喃 为溶剂， 反应 1.58h， 以86%的产率得到(methylamino)dihydroborane
  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

• 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
• Heterogeneous Dehydrocoupling of Amine–Borane Adducts by Skeletal Nickel Catalysts
  作者：Alasdair P. M. Robertson、Riccardo Suter、Laurent Chabanne、George R. Whittell、Ian Manners

  DOI：10.1021/ic201809g

  日期：2011.12.19

  transition metal. Catalytic dehydrocoupling of Me2NH·BH3 (1) and Et2NH·BH3 (5) was demonstrated using 5 mol % skeletal Ni catalyst at 20 °C and produced [Me2N–BH2]2 (2) and [Et2N–BH2]2/Et2N═BH2 (6), respectively. The related adduct iPr2NH·BH3 (7) was also dehydrogenated to afford iPr2N═BH2 (8) but with significant catalyst deactivation. Catalytic dehydrocoupling of MeNH2·BH3 (9) was found to yield the

  由Ni / Al合金中Al的选择性浸出产生的骨架Ni已成功用于各种胺-硼烷加合物的催化脱氢。低成本和简便的单步合成相结合，使该系统成为先前描述的贵金属和其他第一行金属催化剂的潜在有吸引力的替代品。催化剂的非均质性质有利于方便的产物纯化，这是第一个基于第一行过渡金属的此类系统。使用5 mol％的骨架Ni催化剂在20°C下证明了Me 2 NH·BH 3（1）和Et 2 NH·BH 3（5）的催化脱氢偶联并生成了[Me 2的N- BH 2 ] 2（2）和[等2的N- BH 2 ] 2 / ET 2 N═BH 2（6），分别。相关的加合物i Pr 2 NH·BH 3（7）也被脱氢得到i Pr 2 N = BH 2（8），但催化剂明显失活。发现MeNH 2 ·BH 3（9）催化脱氢反应生成环状三氮杂硼烷[MeNH–BH 2 ] 3（10）为主要产物，而当使用化学计量的Ni时，会形成高分子量聚（甲基氨基硼烷）[MeNH-BH
• Dehydrocoupling Reactions of Secondary and Primary Amine–Borane Adducts Catalyzed by Half-sandwich Carbonyl Complexes, [CpMn(CO)₃], [(η⁶-C₆H₆)Cr(CO)₃], and [CpV(CO)₄]
  作者：Taeko Kakizawa、Yasuro Kawano、Kohsuke Naganeyama、Mamoru Shimoi

  DOI：10.1246/cl.2011.171

  日期：2011.2.5

  Dehydrocoupling reactions of amine–borane adducts catalyzed by half-sandwich carbonyl complexes are described. Secondary amine–borane adducts released H2 with catalytic action of [CpMn(CO)3] (Cp: η5-C5H5), [(η6-C6H6)Cr(CO)3], and [CpV(CO)4] under photoirradiation to produce dimeric or monomeric aminoboranes. These results were parallel to the [M(CO)6]-catalyzed system (M = Cr, Mo, and W); however, the reactions were considerably slower. Dehydrocoupling of BH3·NH2Me afforded an aminoborane polymer, [BH2NHMe]n.

  介绍了在半三明治羰基复合物催化下胺硼烷加合物的脱氢偶联反应。在[CpMn(CO)3]（Cp：η5-C5H5）、[(η6-C6H6)Cr(CO)3]和[CpV(CO)4]的催化作用下，仲胺硼烷加合物在光照射下释放出 H2，生成二聚或单体氨基硼烷。这些结果与[M(CO)6]催化体系（M = Cr、Mo 和 W）相似，但反应速度要慢得多。BH3-NH2Me 的脱氢偶联生成了氨基硼烷聚合物 [BH2NHMe]n。
• Aluminum borate nanowires from the pyrolysis of polyaminoborane precursors
  作者：Van An Du、Titel Jurca、George R. Whittell、Ian Manners

  DOI：10.1039/c5dt03324a

  日期：——

  [N(R)H-BH2]n (1: R = H, 2: R = Me) were pyrolyzed on a range of substrates: silicon, metal foils (stainless steel, nickel, and rhodium), and sapphire wafers, as well as on Al2O3 and AlN powders. The pyrolysis of 2 on a Si-wafer resulted in porous nanostructures containing hexagonal-boron nitride (h-BN). In the case of 1 or H3N·BH3 as precursor, using rhodium foil as substrate afforded amorphous B and N-containing

  聚氨基硼烷[N（R）H-BH 2 ] n（1：R = H，2：R = Me）在一系列衬底上热解：硅，金属箔（不锈钢，镍和铑）和蓝宝石晶片以及Al 2 O 3和AlN粉末。2在硅晶片上的热解产生了包含六方氮化硼（h-BN）的多孔纳米结构。在以1或H 3 N·BH 3为前体的情况下，使用铑箔作为基材，分别得到非晶态的含B和N的纳米结构，以及多分散的球形纳米粒子。将基板切换为蓝宝石晶片和Al 2O 3或AlN粉末会导致形成晶体Al 5 BO 9纳米结构（纳米线，纳米管和纳米带）。对于蓝宝石晶片，通过改变表面缺陷密度来影响所得纳米线的尺寸。
• Iridium-Catalyzed Dehydrogenation of Substituted Amine Boranes: Kinetics, Thermodynamics, and Implications for Hydrogen Storage
  作者：Brandon L. Dietrich、Karen I. Goldberg、D. Michael Heinekey、Tom Autrey、John C. Linehan

  DOI：10.1021/ic801161g

  日期：2008.10.6

  Dehydrogenation of amine boranes is catalyzed efficiently by the iridium pincer complex (kappa (3)-1,3-(OP ( t )Bu 2) 2C 6H 3)Ir(H) 2 ( 1). With CH 3NH 2BH 3 (MeAB) and with AB/MeAB mixtures (AB = NH 3BH 3), the rapid release of 1 equiv of H 2 is observed to yield soluble oligomeric products at rates similar to those previously reported for the dehydrogenation of AB catalyzed by 1. Delta H for the

  铱钳子络合物（kappa（3）-1,3-（OP（t）Bu 2）2C 6H 3）Ir（H）2（1）有效地催化胺硼烷的脱氢。使用CH 3NH 2BH 3（MeAB）和AB / MeAB混合物（AB = NH 3BH 3），观察到1当量H 2的快速释放以类似于先前报道的AB脱氢速率产生可溶的低聚产物。由量热法测定了由1.δH催化的AB，MeAB和AB / MeAB混合物的脱氢反应。将反应的实验热与计算研究的结果进行比较。