Marquardt Christian, Hegen Oliver, Vogel Ariane, Stauber Andreas, Bodensteiner Michael, Timoshkin Alexey Y, Scheer Manfred
Institut für Anorganische Chemie, Universität Regensburg, 93040, Regensburg, Germany.
Institute of Chemistry, St. Petersburg State University, 199034 Universitetskaya emb. 7/9, St. Petersburg, Russia.
Chemistry. 2018 Jan 9;24(2):360-363. doi: 10.1002/chem.201705510. Epub 2017 Dec 6.
We report on depolymerization reactions of poly(phosphinoboranes). The cleavage of the polymers [H PBH ] (2 a), [tBuHPBH ] (2 c), [PhHPBH ] (2 e) and the oligomer [Ph PBH ] (2 b), with strong Lewis bases (LBs), in particular with NHCs, leads to the corresponding monomeric phosphanylboranes R R PBH LB. It is observed that the depolymerization depends on the strength and stability of the LBs as well as on the substitution pattern of the poly(phosphinoboranes). The solid state structures of the monomeric phosphinoboranes H PBH NHC (NHC=N-heterocyclic carbene) (4 a), H PBH NHC (5 a) and tBuHPBH NHC (4 c) were determined. DFT calculations support the experimentally observed reaction behavior.
我们报道了聚（膦硼烷）的解聚反应。聚合物[H PBH ]（2 a）、[tBuHPBH ]（2 c）、[PhHPBH ]（2 e）以及低聚物[Ph PBH ]（2 b）与强路易斯碱（LBs），特别是与氮杂环卡宾（NHCs）发生裂解反应，生成相应的单体膦硼烷R R PBH LB。据观察，解聚反应取决于路易斯碱的强度和稳定性以及聚（膦硼烷）的取代模式。测定了单体膦硼烷H PBH NHC（NHC = N-杂环卡宾）（4 a）、H PBH NHC（5 a）和tBuHPBH NHC（4 c）的固态结构。密度泛函理论（DFT）计算支持了实验观察到的反应行为。
