Catalytic redistribution and polymerization of diborazanes: unexpected observation of metal-free hydrogen transfer between aminoboranes and amine-boranes.
Catalytic redistribution and polymerization of diborazanes: unexpected observation of metal-free hydrogen transfer between aminoboranes and amine-boranes.
复制标题
DOI：
10.1021/ja208752w
复制
发表时间：
2011-11
影响因子：
15
通讯作者：
A. Robertson;E. Leitao;I. Manners
中科院分区：
文献类型：
--
作者：
A. Robertson;E. Leitao;I. Manners
线性二硼氮烷MeNH（2）-BH（2）-NHMe-BH（3）的Ir催化（20 °C）或热（70 °C）脱氢偶联导致形成聚或低聚氨基硼烷[MeNH-BH（2）]（x）（x = 3至>1000）通过初始再分布过程形成MeNH（2）·BH（3）以及瞬时MeNH·BH（2），其主要以金属结合和游离形式存在，分别对类似化学的研究发现，在用二硼氮烷Me（3）N-BH（2）-NHMe-BH（3）或胺-硼烷RR'NH·BH（3）（R，R' = H或Me）处理后，“模型”氨基硼烷iPr（2）N-BH（2）中的B N键发生无金属氢化，生成iPr（2）NH·BH（3）。
Ir-catalyzed (20 °C) or thermal (70 °C) dehydrocoupling of the linear diborazane MeNH(2)-BH(2)-NHMe-BH(3) led to the formation of poly- or oligoaminoboranes [MeNH-BH(2)](x) (x = 3 to >1000) via an initial redistribution process that forms MeNH(2)·BH(3) and also transient MeNH═BH(2), 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═BH(2) to give iPr(2)NH·BH(3) upon treatment with the diborazane Me(3)N-BH(2)-NHMe-BH(3) or amine-boranes RR'NH·BH(3) (R, R' = H or Me).