Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 59, Issue 12, Pages 4897-4901Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201916073
Keywords
aluminium; aluminyl reagent; carbon monoxide; imide; small molecule activation
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Funding
- Leverhulme Trust [F/08699/E]
- Academy of Finland [314794]
- Academy of Finland (AKA) [314794, 314794] Funding Source: Academy of Finland (AKA)
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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-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene; Dipp=2,6-diisopropylphenyl) structural characterization by X-ray crystallography reveals a short Al-N distance, which is thought primarily to be due 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 equivalent to O bond cleavage. Thermodynamically, this is driven, at least in part, by Al-O bond formation. Mechanistically, a combination of quantum chemical and experimental observations suggests that the reaction proceeds via exchange of the NR and O substituents through intermediates featuring an aluminium-bound isocyanate fragment.
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