Bläsing Kevin, Bresien Jonas, Labbow René, Michalik Dirk, Schulz Axel, Thomas Max, Villinger Alexander
Anorganische Chemie, Institut für Chemie, Universität Rostock, A.-Einstein-Str. 3a, 18059, Rostock, Germany.
Materialdesign, Leibniz-Institut für Katalyse an der Universität Rostock, A.-Einstein-Str. 29a, 18059, Rostock, Germany.
Angew Chem Int Ed Engl. 2019 May 13;58(20):6540-6544. doi: 10.1002/anie.201902226. Epub 2019 Apr 4.
The reaction of HN with the strong Lewis acid B(C F ) led to the formation of a very labile HN ⋅B(C F ) adduct, which decomposed to an aminoborane, H(C F )NB(C F ) , above -20 °C with release of molecular nitrogen and simultaneous migration of a C F group from boron to the nitrogen atom. The intermediary formation of azide-borane adducts with B(C F ) was also demonstrated for a series of organic azides, RN (R=Me Si, Ph, 3,5-(CF ) C H ), which also underwent Staudinger-like decomposition along with C F group migration. In accord with experiment, computations revealed rather small barriers towards nitrogen release for these highly labile azide adducts for all organic substituents except R=Me Si (m.p. 120 °C, T =189 °C). Hydrolysis of the aminoboranes provided C F -substituted amines, HN(R)(C F ), in good yields.
HN与强路易斯酸B(CF)反应生成了一种非常不稳定的HN·B(CF)加合物，该加合物在-20°C以上分解为氨基硼烷H(CF)NB(CF)，同时释放出分子氮，并且一个CF基团从硼原子迁移至氮原子。对于一系列有机叠氮化物RN（R = MeSi、Ph、3,5-(CF)C6H），也证明了会与B(CF)形成叠氮硼烷加合物中间体，这些中间体同样会发生类似施陶丁格的分解反应并伴有CF基团迁移。与实验结果一致，计算表明，除R = MeSi（熔点120°C，T = 189°C）外，所有有机取代基的这些高度不稳定叠氮加合物释放氮的能垒都相当小。氨基硼烷水解可高产率地得到CF取代的胺HN(R)(CF)。
