Carbon Monoxide Activation by a Molecular Aluminium Imide : C‐O Bond Cleavage and C‐C Bond Formation
Heilmann, A., Hicks, J., Vasko, P., Goicoechea, J., & Aldridge, S. (2020). Carbon Monoxide Activation by a Molecular Aluminium Imide : C‐O Bond Cleavage and C‐C Bond Formation. Angewandte Chemie, 591(12), 4897-4901. https://doi.org/10.1002/anie.201916073
Julkaistu sarjassa
Angewandte ChemiePäivämäärä
2020Tekijänoikeudet
© 2020 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim
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 = 4,5‐bis(2,6‐di iso propylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethyl‐xanthene; Dipp = 2,6‐di iso propylphenyl) structural characterization by X‐ray crystallography reveals a short Al‐N distance, which is thought to be due primarily to the low coordinate nature of the nitrogen centre. The Al‐N unit is highly polar, and capable of the activation of relatively inert chemical bonds, such as those found in dihydrogen and carbon monoxide. In the case of CO, uptake of two molecules of the substrate leads to C‐C coupling and C º O bond cleavage. Thermodynamically, this is driven – at least in part – by Al‐O bond formation. Mechanist‐ically, a combination of quantum chemical and experimental observations suggest that the reaction proceeds via exchange of the NR and O substituents through intermediates featuring an aluminium‐bound isocyanate fragment.
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Wiley-VCH VerlagISSN Hae Julkaisufoorumista
1433-7851Asiasanat
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https://converis.jyu.fi/converis/portal/detail/Publication/34503839
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We thank the Leverhulme Trust (F/08699/E) for funding aspects of this work. PV thanks the Academy of Finland (Grant No. 314794).Lisenssi
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