Highly electron-rich β-diketiminato systems: synthesis and coordination chemistry of amino-functionalized “N-nacnac” ligands

Dinh Cao Huan Do, Ailsa Keyser, Andrey V. Protchenko, Brant Maitland, Indrek Pernik, Haoyu Niu, Eugene L. Kolychev, Arnab Rit, Dragoslav Vidovic, Andreas Stasch*, Cameron Jones, Simon Aldridge

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

34 Citations (Scopus)


The synthesis of a class of electron-rich amino-functionalized β-diketiminato (N-nacnac) ligands is reported, with two synthetic methodologies having been developed for systems bearing backbone NMe2 or NEt2 groups and a range of N-bound aryl substituents. In contrast to their (Nacnac)H counterparts, the structures of the protio-ligands feature the bis(imine) tautomer and a backbone CH2 group. Direct metalation with lithium, magnesium, or aluminium alkyls allows access to the respective metal complexes through deprotonation of the methylene function; in each case X-ray structures are consistent with a delocalized imino-amide ligand description. Transmetalation using lithium N-nacnac complexes is then exploited to access p- and f-block metal complexes, which allow for like-for-like benchmarking of the N-nacnac ligand family against their more familiar Nacnac counterparts. In the case of SnII, the degree of electronic perturbation effected by introduction of the backbone NR2 groups appears to be constrained by the inability of the amino group to achieve effective conjugation with the N2C3 heterocycle. More obvious divergence from established structural norms is observed for complexes of the harder YbII ion, with azaallyl/imino and even azaallyl/NMe2 coordination modes being demonstrated by X-ray crystallography.

Original languageEnglish
Pages (from-to)5830-5841
Number of pages12
JournalChemistry - A European Journal
Issue number24
Publication statusPublished - 27 Apr 2017
Externally publishedYes


  • coordination chemistry
  • electron-rich compounds
  • ligand design
  • main group chemistry
  • nacnac ligands


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