Wang Long, Samigullin Kamil, Wagner Matthias, McQuilken Alison C, Warren Timothy H, Daniliuc Constantin G, Kehr Gerald, Erker Gerhard
Organisch-Chemisches Institut, Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Straße 7, 60438, Frankfurt (Main), Germany.
Chemistry. 2016 Jul 25;22(31):11015-21. doi: 10.1002/chem.201601583. Epub 2016 Jun 29.
Hydroboration of dimesitylvinylphosphane with bis[3,5-bis(trifluoromethyl)phenyl]borane [HB(Fxyl)2 ] gave the intramolecular ethylene-bridged P/B frustrated Lewis pair (FLP) Mes2 PCH2 CH2 B(Fxyl)2 . The new compound underwent a variety of typical FLP reactions such as P/B-addition to the carbonyl group of p-chloro-benzaldehyde. Cooperative N,N-addition to nitric oxide gave the respective persistent P/B FLPNO(.) radical, which readily reacted with 1,4-cyclohexadiene by H-atom abstraction to yield the corresponding P/B FLPNOH product. The B(Fxyl)2 -containing FLP reacted as a template for the HB(C6 F5 )2 reduction of carbon monoxide to the formyl stage to give the respective FLP(η(2) -formylborane) product. Most products were characterized by single-crystal X-ray crystal structure analysis.
用双[3,5-双（三氟甲基）苯基]硼烷[HB(Fxyl)₂]对二甲基乙烯基膦进行硼氢化反应，得到分子内乙烯桥连的P/B受阻路易斯对（FLP）Mes₂PCH₂CH₂B(Fxyl)₂。该新化合物经历了多种典型的FLP反应，如对对氯苯甲醛羰基的P/B加成。与一氧化氮的协同N,N加成得到相应的持久性P/B FLPNO(·)自由基，该自由基通过氢原子夺取与1,4-环己二烯 readily反应，生成相应的P/B FLPNOH产物。含B(Fxyl)₂的FLP作为模板，用于将一氧化碳还原到甲酰基阶段，得到相应的FLP(η²-甲酰基硼烷)产物。大多数产物通过单晶X射线晶体结构分析进行了表征。
