Backbone Reactivity of Lithium β-Diketiminate (NacNac) Complexes with CO₂ , tBuNCO and iPrNCO

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 CO₂ gives an eight-atom carboxylate (Li₂ O₄ C₂ ) 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.