Weinhart Michael A K, Seidl Michael, Timoshkin Alexey Y, Scheer Manfred
Institut für Anorganische Chemie, Universität Regensburg, 93040, Regensburg, Germany.
Institute of Chemistry, Saint Petersburg State University, Universitetskaya emb. 7/9, 199034, St. Petersburg, Russia.
Angew Chem Int Ed Engl. 2021 Feb 15;60(7):3806-3811. doi: 10.1002/anie.202013849. Epub 2020 Dec 15.
The synthesis and characterization of the unprecedented compounds IDipp⋅E'H AsH (E'=Al, Ga; IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) are reported, the first monomeric, parent representatives of an arsanylalane and arsanylgallane, respectively, stabilized only by a LB (LB=Lewis Base). They are prepared by a salt metathesis reaction of KAsH with IDipp⋅E'H Cl (E'=Al, Ga). The H -elimination pathway through the reaction of AsH with IDipp⋅E'H (E'=Al, Ga) was found to be a possible synthetic route with some disadvantages compared to the salt metathesis reaction. The corresponding organo-substituted compounds IDipp⋅GaH AsPh (1) and IDipp⋅AlH AsPh (2) were obtained by the reaction of KAsPh with IDipp⋅E'H Cl (E'=Al, Ga). The novel branched parent compounds IDipp⋅E'H(EH ) (E'=Al, Ga; E=P, As) were synthesized by salt metathesis reactions starting from IDipp⋅E'HCl (E'=Al, Ga). Supporting DFT computations give insight into the different synthetic pathways and the stability of the products.
报道了前所未有的化合物IDipp⋅E'H AsH（E' = Al，Ga；IDipp = 1,3 - 双（2,6 - 二异丙基苯基）咪唑啉 - 2 - 亚基）的合成与表征，它们分别是仅由一个路易斯碱（LB）稳定的首个单体型原代芳基砷基铝烷和芳基砷基镓烷。它们通过KAsH与IDipp⋅E'H Cl（E' = Al，Ga）的盐复分解反应制备。与盐复分解反应相比，发现通过AsH与IDipp⋅E'H（E' = Al，Ga）反应的氢消除途径是一条可能的合成路线，但存在一些缺点。通过KAsPh与IDipp⋅E'H Cl（E' = Al，Ga）反应得到了相应的有机取代化合物IDipp⋅GaH AsPh（1）和IDipp⋅AlH AsPh（2）。通过从IDipp⋅E'HCl（E' = Al，Ga）开始的盐复分解反应合成了新型支链原代化合物IDipp⋅E'H(EH )（E' = Al，Ga；E = P，As）。支持性的密度泛函理论计算深入了解了不同的合成途径和产物的稳定性。
