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

Richard M. Gauld, Ross McLellan, Alan R. Kennedy, Jim Barker, Jacqueline Reid, Robert E. Mulvey

Research output: Contribution to journalArticle

4 Citations (Scopus)
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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.

Original languageEnglish
Pages (from-to)14728-14734
Number of pages7
JournalChemistry - A European Journal
Volume25
Issue number64
Early online date1 Oct 2019
DOIs
Publication statusPublished - 18 Nov 2019

Keywords

  • β-diketiminates
  • carbon dioxide fixation
  • isocyanates
  • lithium
  • x-ray diffraction

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