Kallmeier Fabian, Nelmes Gareth R, McMullin Claire L, Edwards Alison J, Hicks Jamie
Research School of Chemistry, Australian National University ACT 2601 Australia
Australian Centre for Neutron Scattering, Australian Nuclear Science and Technology Organisation New Illawarra Road, Lucas Heights NSW 2234 Australia.
Chem Sci. 2025 May 13. doi: 10.1039/d5sc02682b.
Anionic aluminium(i) complexes, or aluminyl anions, are a recently discovered class of main group compounds that can C-H activate simple aromatic molecules. However, functional group tolerance remains an issue, with the activation of functionalised arenes often favouring more kinetically accessible side reactions ( C-O/C-F activation) over the desired C-H activation. Here, we report a new, electron-rich potassium aluminyl complex, which by DFT has been calculated to be the most nucleophilic diamido aluminyl anion reported to date. The anion shows unprecedented rates of reaction towards the C-H activation of arenes, achieving the C-H activation of stoichiometric benzene in seconds at room temperature. Furthermore, the C-H activation is selective even in a range of functionalised arenes, including those with C-O and C-F bonds.
阴离子铝（I）配合物，即铝酰阴离子，是最近发现的一类主族化合物，能够对简单芳香分子进行C-H活化。然而，官能团耐受性仍然是一个问题，官能化芳烃的活化通常更倾向于动力学上更容易发生的副反应（C-O/C-F活化），而不是所需的C-H活化。在此，我们报道了一种新型的富电子钾铝酰配合物，通过密度泛函理论（DFT）计算得出，它是迄今为止报道的亲核性最强的二氨基铝酰阴离子。该阴离子对芳烃的C-H活化显示出前所未有的反应速率，在室温下数秒内就能实现化学计量的苯的C-H活化。此外，即使在一系列官能化芳烃中，包括那些含有C-O和C-F键的芳烃，C-H活化也是具有选择性的。
