Modification of a Common β‐diketiminate NacNac Framework via Sequential Lithiation and Small Molecule Insertion

Abstract A widely utilised class of ligands in synthesis and catalysis, β‐diketiminate (BDI) or NacNac compounds were initially considered innocent in the sense that they remained intact in all their applications. That changed when the γ‐C−H unit of their NCCCN backbone was found to engage in reactions with electrophiles. Here, we show that this special reactivity can be used advantageously to prepare tripodal modifications of the common NacNac ligand derived from 2,6‐diisopropylphenyl‐β‐methyldiketimine [NacNacH (Me, Dipp)]. Lithiation to give NacNacLi, followed by reactions with isocyanates, isothiocyanates and a carbodiimide, have afforded a series of tripodal NacNac variants having N,N,N,O; N,N,N,S; or N,N,N,N potential dentation sites, many of which have been crystallographically characterised. Distinct ligating modes of these new ligands have been elucidated through the crystal structures of their lithiated derivatives.