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Issue 40, 2016
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Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base macrocyclic ligands

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Abstract

Heterodinuclear uranyl/group 14 complexes of the aryl- and anthracenyl-linked Schiff-base macrocyclic ligands LMe and LA were 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 M⋯OUO 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 PbII complex was cleanly accessible although this complex was relatively unstable in the presence of HN(SiMe3)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.

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

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Publication details

The article was received on 16 May 2016, accepted on 21 Jun 2016 and first published on 29 Jun 2016


Article type: Paper
DOI: 10.1039/C6DT01948J
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Dalton Trans., 2016,45, 15902-15909
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    Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base macrocyclic ligands

    N. L. Bell, P. L. Arnold and J. B. Love, Dalton Trans., 2016, 45, 15902
    DOI: 10.1039/C6DT01948J

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