The synthesis and structures of the first heteroleptic β-diketiminato complexes of lead(II) with terminal phenolato, bis(trimethylsilyl)amido, bis(trimethylsilyl)phosphanido and silylidenephosphanido ligands are reported; 207Pb NMR spectroscopic data indicate that lead(II) can serve as a Ï-donor or acceptor centre, depending on the electronegativity of the terminal ligand.