Backbone reactivity of lithium β-Diketiminate (NacNac) complexes with CO 2, tBuNCO and iPrNCO

Gauld, Richard M. and McLellan, Ross and Kennedy, Alan R. and Barker, Jim and Reid, Jacqueline and Mulvey, Robert E. (2019) Backbone reactivity of lithium β-Diketiminate (NacNac) complexes with CO 2, tBuNCO and iPrNCO. Chemistry - A European Journal, 25 (64). pp. 14728-14734. ISSN 1521-3765 (https://doi.org/10.1002/chem.201904013)

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Abstract

Though alkali metal NacNac (β-diketiminate) complexes have been utilised in synthesis as NacNac-transfer agents, studies of them in their own right with small molecules are exceptionally rare. Here, the lithium compound of the common 2,6-diisopropylphenyl-β-methyldiketiminate [NacNac(Dipp, Me)] ligand is investigated with carbon dioxide and isocyanates. In all four cases reaction occurs at the backbone γ-C atom of the NacNac ligand, which redistributes electronically into a diimine. Insertion of CO 2 gives an eight-atom carboxylate (Li 2O 4C 2) ring at the γ-C site in a dimer. Insertion of tBuNCO gives a secondary amide at the γ-C site in a monomer with TMEDA chelating lithium. Double insertion of tBuNCO and (adventitious) oxygen gives a dimer with a (LiO) 2 central core involving the latter source. Insertion of less bulky (iPrNCO) gives a dimer with dimerisation through the C=O bonds of the emergent secondary amide function.

ORCID iDs

Gauld, Richard M., McLellan, Ross ORCID logoORCID: https://orcid.org/0000-0001-9700-0258, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Barker, Jim, Reid, Jacqueline and Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564;
  • Item type:Article
    ID code:70059
    Dates:
    Date
    Event
    18 November 2019
    Published
    1 October 2019
    Published Online
    30 September 2019
    Accepted
    Notes:This is the peer reviewed version of the following article: Gauld, RM, McLellan, R, Kennedy, AR, Barker, J, Reid, J & Mulvey, RM 2019, 'Backbone reactivity of the lithium β-diketiminate (NacNac) complexes with CO2, t-BuNCO and iPr-NCO' Chemistry - A European Journal, which has been published in final form at https://doi.org/10.1002/chem.201904013. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:08 Oct 2019 13:54
    Last modified:11 Nov 2024 12:27
    URI:https://strathprints.strath.ac.uk/id/eprint/70059
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