Coordination of β-Ketoimine-Derived Ligands at Main Group and Transition Metals

The β-ketoimine HC[MeC(O)][MeC(NHt-Bu)] (1H) (Me = methyl) was used as a ligand in the synthesis of organo-aluminium and gallium compounds. With Al, the NH functionality was deprotonated to form the N,O-chelating β-ketoiminate ligand in Al{HC[MeC(O)][MeC(Nt-Bu)]}Me2 (3) (t-Bu = tertiary butyl), whereas the neutral form coordinated to trimethylgallium via the oxygen atom to form the adduct GaMe3·{HC[MeC(O)][MeC(NHt-Bu)]} (4). Reaction of 1H with Ar†NH2 (Ar† = 2-t-BuC6H4) afforded the new N-aryl β-ketoimine HC[MeC(O)][MeC(NHAr†)] (2H), which reacted with Pd(OAc)2 (OAc = acetate = CH3CO2–) to afford the heteroleptic dimer {Pd[HC(MeC(O))(MeC(NAr†))](μ-OAc)}2 ([5]2). The homoleptic bis(β-ketoiminate) Pd{HC[MeC(O)][MeC(NAr†)]}2 (6) was isolated as a minor product of this reaction. The crystal structures of compounds 3, 4, [5]2, and 6 are reported.