Issue 40, 2016

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 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

Supplementary files

Article information

Article type
Paper
Submitted
16 May 2016
Accepted
21 Jun 2016
First published
29 Jun 2016
This article is Open Access
Creative Commons BY license

Dalton Trans., 2016,45, 15902-15909

Author version available

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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