环三硼烷 | 13871-09-5

• 中文名称: 环三硼烷
• 英文名称: cyclotriborane
• 英文别名: cyclotriborazane；1,3,5-Triazonia-2,4,6-triboranuidacyclohexane
• CAS: 13871-09-5
• 化学式: B₃H₁₂N₃
• 分子量: 86.5484
• InChiKey: IDQLXTFHZTXEDE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -7.31
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  49.8
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  环三硼烷 以 neat (no solvent) 为溶剂， 生成 poly(boron amide imide)
  参考文献：
  名称：

  Thermal decomposition of cyclotriborazane

  摘要：

  Cyclotriborazane (CTB), B3N3H12, is a crystalline white solid, which decomposes above 400 K to hydrogen and a few other products, depending on the reaction conditions. In this work we present investigations of the thermal decomposition of both the neat compound and CTB dissolved in diglyme and tetraglyme. Several thermophysical and analytical methods, such as differential scanning calorimetry (DSC), thermogravimetry (TG), mass spectroscopy (QMS), and B-11 nuclear magnetic resonance spectroscopy (NMR) have been used for this investigation. The decomposition of the neat substance releases 3.1 mol H-2/mol CTB and leads to a polymeric products and borazine. In open vessels, sublimation as a competing process also occurs. The enthalpy of the decomposition process (Delta H-R(s)) has been determined as Delta H-R(s), = -34.0 +/- 2.9 kJ/mol. In contrast to the thermal decomposition of the pure substance, the decomposition in polyethers, such as diglyme and tetraglyme, leads above 370 K to borazine and small amounts of soluble oligomeric borazine species. Also BH3 group containing species are occurring as intermediates. In these systems no precipitation was detected. DSC measurements show for the decomposition in solution several strong exothermic effects. The overall decomposition enthalpy in diglyme is given by Delta H-R(d) = -32.0 +/- 2.8 kJ/mol and in tetraglyme by Delta H-R(0) = -48.0 +/- 4.7 kJ/mol. The enthalpy of solution of cyclotriborazane was determined in diglyme and in tetraglyme with the values Delta H-D(d) = -2.1 +/- 0.2 kJ/mol and Delta H-D(t) = -4.6 +/- 0.5 kJ/mol, respectively. (C) 2007 Elsevier B.V.. All rights reserved.

  DOI：

  10.1016/j.tca.2007.03.006
• 作为产物：
  描述：

  硼烷铵络合物 在 ((1,3-C5H3(SiMe3)2)2Ti)2(μ2:η1,η1-N2) 作用下， 以 四氢呋喃 为溶剂， 生成 环三硼烷
  参考文献：
  名称：

  Amineborane dehydrogenation promoted by isolable zirconium sandwich, titanium sandwich and N2 complexes

  摘要：

  报告了双(环戊二烯基)钛和双(茚基)锆化合物家族促进 R2NHBH3（R = Me，H）催化脱氢的情况；研究了结构-反应关系与环戊二烯基和茚基取代基的函数关系。

  DOI：

  10.1039/b704941b

文献信息

• Synthetic and mechanistic studies of metal-free transfer hydrogenations applying polarized olefins as hydrogen acceptors and amine borane adducts as hydrogen donors
  作者：Xianghua Yang、Thomas Fox、Heinz Berke

  DOI：10.1039/c1ob06381b

  日期：——

  spectroscopy. Deuterium kinetic isotope effects and the traced hydroboration intermediate revealed that the double H transfer process occurred regio-specifically in two steps with hydride before proton transfer characteristics. Studies on substituent effects and Hammett correlation indicated that the rate determining step of the HN transfer is in agreement with a concerted transition state. The very reactive intermediate

  极化烯烃的无金属转移氢化（RR'C CEE'：R，R'= H或有机基，E，E'= CN或 CO 2我）使用胺硼烷加合物 RR'NH–BH 3（R = R'= H，AB ; R = Me，R'= H，人与生物圈; R = t Bu，R'= H，tBAB; R = R′=我，DMAB通过原位NMR光谱研究作为氢供体的H 2O。氘 动力学同位素效应和所追踪的硼氢化中间体表明，双H转移过程在两个步骤中都发生了区域特异性反应 氢化物质子转移前的特征。对取代基效应和Hammett相关性的研究表明，^ h ñ转移与一致的过渡状态相一致。由AB生成的非常活泼的中间体[NH 2 BH 2 ]通过添加二甲醚被捕集环己烯 进入反应混合物形成 Cy 2 BNH 2。最终产品硼嗪假定（BHNH）3是通过[NH 2 BH 2 ]或其溶剂稳定的衍生物[NH 2 BH 2 ]-（溶剂）脱氢偶联形成的，而不是通过环三硼烷[NH
• 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
• Amine Boranes Dehydrogenation Mediated by an Unsymmetrical Iridium Pincer Hydride: (PCN) vs (PCP) Improved Catalytic Performance
  作者：Lapo Luconi、Elena S. Osipova、Giuliano Giambastiani、Maurizio Peruzzini、Andrea Rossin、Natalia V. Belkova、Oleg A. Filippov、Ekaterina M. Titova、Alexander A. Pavlov、Elena S. Shubina

  DOI：10.1021/acs.organomet.8b00488

  日期：2018.9.24

  process; it is detected by a variable-temperature multinuclear NMR of the reaction course (in the 190–323 K range). A DFT modeling of the reaction mechanism using DMAB as substrate has been performed with the geometry optimization in toluene at the M06 level of theory. The combination of the kinetic and computational data reveals that a simultaneous B–H/N–H activation occurs in the presence of 1, after

  Ir III氢化物（t Bu PCN）IrHCl（1）包含三登酸酯不对称钳位配体t Bu PCN – t Bu PCN（H）= 1- [3-[（二叔丁基膦基）甲基]苯基] -1 H-吡唑}已在环境温度下用作四氢呋喃溶液中的氨硼烷（NH 3 BH 3，AB）和胺硼烷脱氢催化剂。1释放一个H 2相当于每AB当量，同时形成环状聚（氨基硼烷）[B-（环三氮杂硼烷基）-胺-硼烷（BCTB）和环三氮杂硼烷（CTB）]作为最终的“乏燃料”。1被发现比其对称类似物（t Bu PCP）IrHCl具有更好的催化活性，在环境温度下记录的TOF值为580 h –1（在THF中为AB）和401 h –1（在甲苯中为DMAB）。通过多核[ 11 B，31 P 1 H}，11H NMR和IR光谱，动力学速率测量和氘化AB同位素同系物的动力学同位素效应测定。氢化/氢硼化中间体（吨卜PCN）IRH（η 2 -BH
• Development of Rhenium Catalysts for Amine Borane Dehydrocoupling and Transfer Hydrogenation of Olefins
  作者：Yanfeng Jiang、Olivier Blacque、Thomas Fox、Christian M. Frech、Heinz Berke

  DOI：10.1021/om900458e

  日期：2009.9.28

  activities. Mechanistic studies were carried out indicating that these rhenium(I) hydride catalyses allowed formation of dihydrogen hydride complexes. A plausible catalytic cycle for both dehydrocoupling and transfer hydrogenation was proposed, which implies the ability of rhenium(I) complexes to activate B−H and N−H bonds by the facile redox interplay of Re(I) and Re(III) species.

  [Re（Br）（H）（NO）（PR 3）2 ] [R = Cy 2a，i Pr 2b）型五配位氢化（（I）络合物是由[Re（Br）2（NO ）（PR 3）2（η 2 -H 2）]（R =赛扬1a中，我镨1B）经由η的去质子化2 -H 2配体与各种碱。通过各种体积较小的两电子供体填充2a或2b的空位，生成18电子配合物[Re（Br）（H）（NO）（PR 3）2（L）]（L = O 2 3，CH 2 = CH 2 4，乙炔5，H 2 6，CO 7，CH 3 CN 8）。研究了反式配位体对Re-H键的影响。氢化物的1 H NMR化学位移取决于L，顺序为O 2 >乙炔> CH 2 = CH 2 > H 2 > CO> CH 3 CN。的反应图2a或2b的与IMES或SIMES配位体提供的五配位络合物[回复（BR）（H）（NO）（PR3）（NHC）]（NHC = IMES 9（IMES = 1,3-bis（2
• Transition Metal-Catalyzed Formation of Boron−Nitrogen Bonds:  Catalytic Dehydrocoupling of Amine-Borane Adducts to Form Aminoboranes and Borazines
  作者：Cory A. Jaska、Karen Temple、Alan J. Lough、Ian Manners

  DOI：10.1021/ja030160l

  日期：2003.8.1

  dehydrocoupling of Me(2)NH.BH(3) was also demonstrated. This new catalytic method was extended to other secondary adducts RR'NH.BH(3) which afforded the dimeric species [(1,4-C(4)H(8))N-BH(2)](2) (2) and [PhCH(2)(Me)N-BH(2)](2) (3) or the monomeric aminoborane (i)Pr(2)N=BH(2) (4) under mild conditions. A new synthetic approach to the linear compounds R(2)NH-BH(2)-NR(2)-BH(3) (5: R = Me; 6: R = 1,4-C(4)H(8)) was

  使用后过渡金属配合物作为预催化剂，开发了一种温和的催化脱氢偶联途径，从伯胺或仲胺-硼烷加合物生成氨基硼烷和环硼氮烷衍生物。加合物 Me(2)NH.BH(3) 在 130 摄氏度的冷凝相中热消除氢，以提供 [Me(2)N-BH(2)](2) (1)。分子间过程的证据，而不是形成 Me(2)N=BH(2) 作为中间体的分子内反应，来自“热管”实验，其中气态 Me(2)NH.BH(3) 没有明显的脱氢偶联) 在 150-450 摄氏度的范围内检测到。 Me(2)NH.BH(3) 的脱氢偶联被发现由 0.5 mol % [Rh(1,5-cod)(mu-Cl)]( 2) 在 25 摄氏度的溶液中，在约 1 小时后定量给出 1。8 小时。如果温度升高或催化剂负载量增加，则脱氢偶联速率显着提高。还证明了各种其他过渡金属配合物（Ir、Ru、Pd）对 Me(2)NH.BH(3) 脱氢偶联的催化活性。这种新的催化方法被扩展到其他二级加合物