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Heterodinuclear uranyl/group 14 complexes of the aryl- and anthracenyl-linked Schiff-base macrocyclic ligands L Me and L A were synthesised by reaction of UO 2 (H 2 L) with M{N(SiMe 3 ) 2 } 2 (M = Ge, Sn, Pb). For complexes of the anthracenyl-linked ligand (L A ) the group 14 metal sits out of the N 4 -donor plane by up to 0.7 Å resulting in relatively short MOUO distances which decrease down the group; however, the solid state structures and IR spectroscopic analyses suggest little interaction occurs between the oxo and group 14 metal. In contrast, the smaller aryl-linked ligand (L Me ) enforces greater interaction between the metals; only the Pb II complex was cleanly accessible although this complex was relatively unstable in the presence of HN(SiMe 3 ) 2 and some organic oxidants. In this case, the equatorial coordination of pyridine-N-oxide causes a 0.08 Å elongation of the endo UO bond and a clear interaction of the uranyl ion with the Pb(ii) cation in the second donor compartment.

Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base macrocyclic ligands