Bakewell Clare, Hobson Katie, Carmalt Claire J
Department of Chemistry, King's College London, 7 Trinity Street, London, SE1 1DB, UK.
Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, UK.
Angew Chem Int Ed Engl. 2022 Aug 1;61(31):e202205901. doi: 10.1002/anie.202205901. Epub 2022 May 17.
The design of new reductive routes to low oxidation state aluminium (Al) compounds offers the opportunity to better understand redox processes at the metal centre and develop reactivity accordingly. Here, a monomeric Al compound acts as a stoichiometric reducing agent towards a series of Al dihydrides, leading to the formation of new low oxidation state species including symmetric and asymmetric dihydrodialanes, and a masked dialumene. These compounds are formed by a series of equilibrium processes involving Al , Al and Al species and product formation can be manipulated by fine-tuning the reaction conditions. The transient formation of monomeric Al compounds is proposed: this is shown to be energetically viable by computational (DFT) investigations and reactivity studies show support for the formation of Al species. Importantly, despite the potential for the equilibrium mixtures to lead to ill-defined reactivity, controlled reactivity of these low oxidation state species is observed.
设计新的低氧化态铝（Al）化合物的还原路线，为更好地理解金属中心的氧化还原过程并据此开发其反应活性提供了契机。在此，一种单体Al化合物作为一系列Al二氢化物的化学计量还原剂，导致形成新的低氧化态物种，包括对称和不对称二氢二铝烷，以及一种掩蔽的二铝烯。这些化合物是通过一系列涉及Al、Al和Al物种的平衡过程形成的，并且产物的形成可以通过微调反应条件来控制。有人提出了单体Al化合物的瞬态形成：通过计算（DFT）研究表明这在能量上是可行的，并且反应活性研究支持Al物种的形成。重要的是，尽管平衡混合物有可能导致反应活性不明确，但仍观察到这些低氧化态物种具有可控的反应活性。
