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

Bell, N. L. , Arnold, P. L. and Love, J. B. (2016) Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base macrocyclic ligands. Dalton Transactions, 45(40), pp. 15902-15909. (doi: 10.1039/C6DT01948J) (PMID:27356021)

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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.

Item Type:Articles
Additional Information:The authors thank the University of Edinburgh and the EPSRC (Grant numbers EP/M010554/1 and EP/H004823/1) for funding.
Glasgow Author(s) Enlighten ID:Bell, Dr Nicola
Authors: Bell, N. L., Arnold, P. L., and Love, J. B.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Dalton Transactions
Publisher:Royal Society of Chemistry
ISSN (Online):1477-9234
Published Online:29 June 2016
Copyright Holders:Copyright © 2016 The Royal Society of Chemistry
First Published:First published in Dalton Transactions 45(40): 15902-15909
Publisher Policy:Reproduced under a Creative Commons License

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