Fischer Malte, Nees Samuel, Kupfer Thomas, Goettel James T, Braunschweig Holger, Hering-Junghans Christian
Leibniz Institut für Katalyse e.V. (LIKAT), A.-Einstein-Str.3a, 18059 Rostock, Germany.
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
J Am Chem Soc. 2021 Mar 24;143(11):4106-4111. doi: 10.1021/jacs.1c00204. Epub 2021 Mar 10.
The combination of (AlCp*), a source of monomeric :AlCp* at elevated temperatures, with TerPnPMe (Pn = P, As), so-called pnicta-Wittig reagents, at 80 °C cleanly gives the pnictaalumenes TerPnAlCp* with polarized Pn-Al double bonds and intramolecular stabilization through interactions of Al with a flanking aryl group of the terphenyl substituent on Pn. In contrast, using TerPPMe, the reaction with 2 equiv of :AlCp or :AlCp* afforded the three-membered 2π-aromatic ring systems TerP(AlCp) ( = 3t, *).
AlCp来源的(AlCp)与所谓的磷叶立德试剂TerPnPMe(Pn = P,As)在80°C下反应,可顺利生成具有极化Pn-Al双键且通过Al与Pn上三联苯取代基的侧翼芳基相互作用实现分子内稳定的磷铝烯TerPnAlCp*。相比之下,使用TerPPMe时,与2当量的:AlCp或:AlCp反应得到了三元2π-芳环体系TerP(AlCp)( = 3t,)。