Evans Matthew J, Neale Samuel E, Anker Mathew D, McMullin Claire L, Coles Martyn P
School of Chemical and Physical Sciences, Victoria University of Wellington, PO Box 600, Wellington, 6012, New Zealand.
Department of Chemistry, University of Bath, Bath, BA2 7AY, UK.
Angew Chem Int Ed Engl. 2022 Apr 11;61(16):e202117396. doi: 10.1002/anie.202117396. Epub 2022 Feb 23.
The potassium aluminyl [K{Al(NON )}] ([NON ] =[O{SiMe NDipp} ] , Dipp=2,6-iPr C H ) activates ethene towards carbonylation with CO under mild conditions. An isolated bis-aluminacyclopropane compound reacted with CO via carbonylation of an Al-C bond, followed by an intramolecular hydrogen shift to form K [Al(NON )(μ-CH CH=CO-1κ C -2κO)Al(NON )Et]. Restricting the chemistry to a mono-aluminium system allowed isolation of [Al(NON )(CH CH CO-κ C )] , which undergoes thermal isomerisation to form the [Al(NON )(CH CH=CHO-κ C,O)] anion. DFT calculations highlight the stabilising influence of incorporated benzene at multiple steps in the reaction pathways.
钾铝烯基化合物[K{Al(NON)}]（[NON]=[O{SiMe₂NDipp}₂]，Dipp = 2,6 - iPr₂C₆H₃）在温和条件下可使乙烯与一氧化碳发生羰基化反应。一种分离得到的双铝环丙烷化合物通过铝 - 碳键的羰基化反应与一氧化碳反应，随后发生分子内氢迁移，形成K[Al(NON)(μ - CH₂CH=CO - 1κC - 2κO)Al(NON)Et]。将化学反应限制在单铝体系中，可以分离得到[Al(NON)(CH₂CH₂CO - κC)]，该化合物会发生热异构化反应，形成[Al(NON)(CH₂CH=CHO - κC,O)]阴离子。密度泛函理论计算结果表明，引入的苯在反应路径的多个步骤中具有稳定作用。
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