Anke Felix, Boye Susanne, Spannenberg Anke, Lederer Albena, Heller Detlef, Beweries Torsten
Leibniz-Institut für Katalyse e.V., Albert-Einstein-Str. 29a, 18059, Rostock, Germany.
Leibniz-Institut für Polymerforschung Dresden, Hohe Str. 6, 01069, Dresden, Germany.
Chemistry. 2020 Jun 23;26(35):7889-7899. doi: 10.1002/chem.202000809. Epub 2020 May 28.
Dehydropolymerisation of methylamine borane (H B⋅NMeH ) using the well-known iron amido complex [(PNP)Fe(H)(CO)] (PNP=N(CH CH PiPr ) ) (1) gives poly(aminoborane)s by a chain-growth mechanism. In toluene, rapid dehydrogenation of H B⋅NMeH following first-order behaviour as a limiting case of a more general underlying Michaelis-Menten kinetics is observed, forming aminoborane H B=NMeH, which selectively couples to give high-molecular-weight poly(aminoborane)s (H BNMeH) and only traces of borazine (HBNMe) by depolymerisation after full conversion. Based on a series of comparative experiments using structurally related Fe catalysts and dimethylamine borane (H B⋅NMe H) polymer formation is proposed to occur by nucleophilic chain growth as reported earlier computationally and experimentally. A silyl functionalised primary borane H B⋅N(CH SiMe )H was studied in homo- and co-dehydropolymerisation reactions to give the first examples for Si containing poly(aminoborane)s.
使用著名的铁酰胺配合物[(PNP)Fe(H)(CO)]（PNP = N(CH₂CH₂PiPr₂)₂）（1）对甲胺硼烷（H₃B·NMeH₂）进行脱氢聚合反应，通过链增长机理生成聚（氨基硼烷）。在甲苯中，观察到H₃B·NMeH₂遵循一级反应行为快速脱氢，这是更一般的米氏动力学的极限情况，生成氨基硼烷H₂B=NMeH，其选择性偶联生成高分子量的聚（氨基硼烷）（H₂BNMeH），完全转化后通过解聚仅生成痕量的硼嗪（HBNMe）。基于一系列使用结构相关铁催化剂的对比实验以及二甲胺硼烷（H₃B·NMe₂H），如之前计算和实验报道的那样，聚合反应被认为是通过亲核链增长发生的。研究了一种硅烷基官能化的伯硼烷H₃B·N(CH₂SiMe₃)H在均相和共脱氢聚合反应中的情况，以得到含硅聚（氨基硼烷）的首个实例。
