B-Methylated Amine-Boranes: Substituent Redistribution, Catalytic Dehydrogenation, and Facile Metal-Free Hydrogen Transfer Reactions
作者:Naomi E. Stubbs、André Schäfer、Alasdair P. M. Robertson、Erin M. Leitao、Titel Jurca、Hazel A. Sparkes、Christopher H. Woodall、Mairi F. Haddow、Ian Manners
DOI:10.1021/acs.inorgchem.5b01946
日期:2015.11.16
dehydrogenation chemistry of amine-boranes substituted at nitrogen has attracted considerable attention, much less is known about the reactivity of their B-substituted analogues. When the B-methylated amine-borane adducts, RR′NH·BH2Me (1a: R = R′ = H; 1b: R = Me, R′ = H; 1c: R = R′ = Me; 1d: R = R′ = iPr), were heated to 70 °C in solution (THF or toluene), redistribution reactions were observed involving
尽管在氮上取代的胺-硼烷的脱氢化学引起了相当大的关注,但对它们的B-取代的类似物的反应性知之甚少。当B-甲基化胺-硼烷加合物时,RR'NH·BH 2 Me(1a:R = R'= H; 1b:R = Me,R'= H; 1c:R = R'= Me; 1d:R = R'= i Pr),在溶液(THF或甲苯)中加热到70°C,观察到重新分布反应,包括硼上甲基和氢取代基的明显扰乱,提供了RR'NH·BH的混合物3– x Me x(x= 0–3)。推测这些反应是通过胺-硼烷离解,然后可逆地形成乙硼烷中间体和加合物重整而发生的。Dehydrocoupling的1A - 1D在THF与铑(I),铱(III)和Ni(0)的预催化剂在20℃下导致的制品阵列,包括氨基硼烷RR'N═BHMe,环状diborazane [RR'N- BHMe] 2和硼嗪[RN–BMe] 3基于原位11 B NMR光谱分析,并通过
Beiträge zur chemie des bors XLVIII. Zur kenntnis von bis(dialkylboryl)aminen
作者:Heinrich Nöth、Heinrich Vahrenkamp
DOI:10.1016/s0022-328x(00)89761-2
日期:1969.3
Diborylamines of the types (R2B)2NH and (R2B)2NR′ (R = CH3, C2H5, C3H7, C4H9;R′ = CH3) are obtained (a) from dialkylhaloboranes and disilazanes, (b) from dialkylhaloboranes and N-metalated aminoboranes, and (c) by aminolysis of dialkyl(mthylthio)boranes. They are thermodynamically unstable with respect to a decomposition into trialkylboranes and borazine derivatives; their decomposition is catalysed
得到(R 2 B)2 NH和(R 2 B)2 NR'(R = CH 3,C 2 H 5,C 3 H 7,C 4 H 9 ; R'= CH 3)类型的二硼胺(a)来自二烷基卤庚烷和二硅氮烷,(b)来自二烷基卤庚烷和N-金属化的氨基硼烷,以及(c)通过二烷基(甲硫基)硼烷的氨解反应)。就分解成三烷基硼烷和硼嗪衍生物而言,它们在热力学上是不稳定的。它们的分解主要是由二烷基卤呋喃酮催化的。