The Aluminyl Anion : A New Generation of Aluminium Nucleophile
Hicks, J., Vasko, P., Goicoechea, J. M., & Aldridge, S. (2021). The Aluminyl Anion : A New Generation of Aluminium Nucleophile. Angewandte Chemie, 60(4), 1702-1713. https://doi.org/10.1002/anie.202007530
Published inAngewandte Chemie
© 2020 WILEY
Trivalent aluminium compounds are well known for their reactivity as Lewis acids/electrophiles, a feature that is exploited in many pharmaceutical, industrial and laboratory-based reactions. Recently, a series of isolable aluminium(I) anions ('aluminyls') have been reported, which offer an alternative to this textbook description: these reagents behave as aluminium nucleophiles. This minireview covers the synthesis, structure and reactivity of aluminyl species reported to date, together with their associated metal complexes. The frontier orbitals of each of these species have been investigated using a common methodology to allow for a like-for-like comparison of their electronic structure and a means of rationalising (sometimes unprecedented) patterns of reactivity.
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Related funder(s)Research Council of Finland
Funding program(s)Postdoctoral Researcher, AoF
Additional information about fundingJH would like to thank the Australian Research Council and the Australian Government for funding aspects of this work (DE190100524). PV thanks the Academy of Finland (Grant No. 314794) and Prof. Heikki M. Tuononen for continued support and computational resources. JMG and SA would also like to thank the Leverhulme Trust (F/08699/E) for funding aspects of this work.
Showing items with similar title or keywords.
Hicks, Jamie; Vasko, Petra; Goicoechea, Jose M.; Aldridge, Simon (Nature Publishing Group, 2018)The reactivity of aluminium compounds is dominated by their electron deficiency and consequent electrophilicity; these compounds are archetypal Lewis acids (electron-pair acceptors). The main industrial roles of aluminium, ...
Hicks, Jamie; Heilmann, Andreas; Vasko, Petra; Goicoechea, Jose; Aldridge, Simon (Wiley-VCH Verlag, 2019)Aluminium oxides constitute an important class of inorganic compound that are widely exploited in the chemical industry as catalysts and catalyst supports. Due to the tendency for such systems to aggregate via Al‐O‐Al ...
Carbon Monoxide Activation by a Molecular Aluminium Imide : C‐O Bond Cleavage and C‐C Bond Formation Heilmann, Andreas; Hicks, Jamie; Vasko, Petra; Goicoechea, Jose; Aldridge, Simon (Wiley-VCH Verlag, 2020)Anionic molecular imide complexes of aluminium are accessible via a rational synthetic approach involving the reactions of organo azides with a potassium aluminyl reagent. In the case of K 2 [( NON )Al(NDipp)] 2 ( NON ...
Arene C‐H activation at aluminium(I) : meta selectivity driven by the electronics of SNAr chemistry Hicks, Jamie; Vasko, Petra; Heilmann, Andreas; Goicoechea, Jose; Aldridge, Simon (Wiley, 2020)The reactivity of the electron-rich anionic Al(I) (‘aluminyl’) compound K 2 [(NON)Al] 2 (NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di- tert -butyl-9,9-dimethylxanthene) towards mono- and disubstituted arenes is reported. ...
Roy, Matthew; Hicks, Jamie; Heilmann, Andreas; Baston, Anne Marie; Vasko, Petra; Goicoechea, Jose; Aldridge, Simon (Wiley-VCH Verlag, 2021)Synthetic routes to lithium, magnesium and zinc aluminyl complexes are reported, allowing for the first structural character-ization of a lithium-aluminium bond. Structural and quantum chemical studies are consistent with ...