Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Chemistry. 2023 Jun 2;29(31):e202300483. doi: 10.1002/chem.202300483. Epub 2023 Apr 20.
The reduction of a carbene-coordinated, sterically encumbered terphenyl-substituted aluminium diiodide, (LRAlI ), yielded a "masked" dialumene (LRAl=AlRL), self-stabilised through [2+2] cycloaddition with a peripheral aromatic group. During the course of the reaction, a carbene-stabilised arylalumylene (LRAl:) was generated in situ, which was trapped using an alkyne, generating an aluminacyclopropene or a C-H activated product thereof, depending on the steric bulk of the alkyne. The masked dialumene also underwent intramolecular cycloreversion and dissociation into alumylene fragments, which reacted with various organic azides to yield monomeric or dimeric iminoalanes depending on the sterics of the azide substituent. The thermodynamics of monomeric and dimeric iminoalane formation were probed by theoretical calculations.
偕二碘取代的卡宾配位、空间位阻较大的三联苯取代的二碘化铝（LRAlI），通过与外围芳香族基团的[2+2]环加成反应，生成了“掩蔽”二烯（LRAl=AlRL），通过[2+2]环加成反应自稳定。在反应过程中，偕二碘取代的卡宾稳定的芳基铝烯（LRAl：）原位生成，并用炔烃捕获，生成铝杂环丙烷或其 C-H 活化产物，这取决于炔烃的空间位阻。掩蔽的二烯也经历分子内环重排和二烯片段的解离，与各种有机叠氮化物反应，根据叠氮取代基的空间位阻，生成单体或二聚亚氨基烷。通过理论计算研究了单体和二聚亚氨基烷形成的热力学。
