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

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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:27 Nov 2024 01:16
    URI:https://strathprints.strath.ac.uk/id/eprint/70059
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