title: Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base macrocyclic ligands.
abstract: Heterodinuclear uranyl/group 14 complexes of the aryl- and anthracenyl-linked Schiff-base macrocyclic ligands LMeand LAwere synthesised by reaction of UO2(H2L) with M{N(SiMe3)2}2(M = Ge, Sn, Pb). For complexes of the anthracenyl-linked ligand (LA) the group 14 metal sits out of the N4-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 (LMe) enforces greater interaction between the metals; only the PbIIcomplex was cleanly accessible although this complex was relatively unstable in the presence of HN(SiMe3)2and 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.
authors.affiliation: EaStCHEM School of chemistry, Joseph Black Building, The King's Buildings, The University of Edinburgh, West Mains Road, Edinburgh EH9 3FJ, UK. jason.love@ed.ac.uk polly.arnold@ed.ac.uk.
authors.forename: Nicola L
authors.initials: NL
authors.lastname: Bell
authors.affiliation: EaStCHEM School of chemistry, Joseph Black Building, The King's Buildings, The University of Edinburgh, West Mains Road, Edinburgh EH9 3FJ, UK. jason.love@ed.ac.uk polly.arnold@ed.ac.uk.
authors.forename: Polly L
authors.initials: PL
authors.lastname: Arnold
authors.affiliation: EaStCHEM School of chemistry, Joseph Black Building, The King's Buildings, The University of Edinburgh, West Mains Road, Edinburgh EH9 3FJ, UK. jason.love@ed.ac.uk polly.arnold@ed.ac.uk.
authors.forename: Jason B
authors.initials: JB
authors.lastname: Love