Reactivity studies and structural outcomes of a bulky dialkylaluminium amide in the presence of the N-Heterocyclic Carbene, ItBu

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Pollard, Victoria A. and Fuentes, Maria-ngeles and Robertson, Stuart D. and Weetman, Catherine and Kennedy, Alan R. and Brownlie, Josh and Angus, Fraser J. and Smylie, Cooper and Mulvey, Robert E. (2021) Reactivity studies and structural outcomes of a bulky dialkylaluminium amide in the presence of the N-Heterocyclic Carbene, ItBu. Polyhedron, 209. 115469. ISSN 0277-5387 (https://doi.org/10.1016/j.poly.2021.115469)

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Abstract

Aluminium reagent iBu2Al(TMP) (TMP is 2,2,6,6-tetramethylpiperidide) has previously shown interesting synergistic metallation chemistry when paired with alkali metal amides. Here its structural chemistry and reactivity is explored in the presence of the N-heterocyclic carbene, ItBu, 1,3-di-tert-butylimidazol-2-ylidene. Abnormal aItBu structures are obtained with iBu2Al(TMP) on its own and in the co-presence of LiTMP, NaTMP or KTMP. Reaction with phenol is stoichiometric dependent leading to the diphenolate [ItBu(H)]+ [(PhO)2Al(iBu)2 and triphenolate [ItBu(H)]+ [(PhO)3Al(iBu)- ionic complexes. Dinuclear aItBu(Ph)C=N[Al(iBu)2N=C(TMP)Ph]Al(iBu)2 was the surprising product from reaction with benzonitrile, displaying an imidoC- and (iBu)2Al- disubstituted imidazolium ring as well as a second imido unit made by addition of "non-nucleophilic" TMP across the benzonitrile triple bond. Potential insight into the mechanism of this intriguing complicated reaction was gained through the crystallographic characterisation of the ketamide [iBu2AlN=C(Ph)TMP]2, a possible intermediate. Reaction with Ph2CHCN, diphenylacetonitrile, proved more straightforward affording the ionic complex [ItBu(H)]+ [Ph2C=C=N]-.

ORCID iDs

Pollard, Victoria A. ORCID logoORCID: https://orcid.org/0000-0002-9149-3458, Fuentes, Maria-ngeles, Robertson, Stuart D. ORCID logoORCID: https://orcid.org/0000-0002-9330-8770, Weetman, Catherine ORCID logoORCID: https://orcid.org/0000-0001-5643-9256, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Brownlie, Josh, Angus, Fraser J., Smylie, Cooper and Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564;
  • Item type:Article
    ID code:77775
    Dates:
    Date
    Event
    22 September 2021
    Published
    15 September 2021
    Published Online
    6 September 2021
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:10 Sep 2021 14:45
    Last modified:12 Dec 2024 11:56
    URI:https://strathprints.strath.ac.uk/id/eprint/77775
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