Divergent Malonamides/Ti(NMe2)4 System for the Synthesis of Mono‐, Bis‐, and Tris(dimethylamide)‐Titanium(IV) Complexes

In the literature, a variety of synthetic methodologies for malonamides (MAs) is informed. The chelating features of MAs have been the subject of extensive investigation for use in liquid extraction of lanthanides (Ln) and actinides (An). However, no comparative study has explored the substituents influence in the nucleophilic behavior of anionic MAs in their role as ligands. Herein, we present unprecedented insight into the divergent 2,2‐dimethyl‐N,N'‐dimesityl‐propanediamide (H2DMDMMA) and 2,2‐dimethyl‐N,N'‐ditert‐butyl‐propanediamide (H2DTDMMA)/ tetrakis(dimethylamido)titanium [Ti(NMe2)4] system, which allowed the collection of five complexes. The titanium amide malonamides obtained have three, two, or one ‐NMe2 group and are cis‐OO' chelated, except for one complex that exhibits the unprecedented cis‐NO chelate mode.