Matthew Gregson
The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes
Gregson, Matthew; Lu, Erli; Mills, David P.; Tuna, Floriana; McInnes, Eric J.L.; Hennig, Christoph; Scheinost, Andreas C.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Kerridge, Andrew; Liddle, Stephen T.
Authors
Erli Lu
David P. Mills
Floriana Tuna
Eric J.L. McInnes
Christoph Hennig
Andreas C. Scheinost
JONATHAN MCMASTER Jonathan.McMaster@nottingham.ac.uk
Professor of Chemistry
William Lewis
Alexander J. Blake
Andrew Kerridge
Stephen T. Liddle
Abstract
© The Author(s) 2017. Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal-ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle.
Citation
Gregson, M., Lu, E., Mills, D. P., Tuna, F., McInnes, E. J., Hennig, C., …Liddle, S. T. (2017). The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes. Nature Communications, 8, Article 14137. https://doi.org/10.1038/ncomms14137
Journal Article Type | Article |
---|---|
Acceptance Date | Dec 2, 2016 |
Online Publication Date | Feb 3, 2017 |
Publication Date | Feb 3, 2017 |
Deposit Date | Mar 9, 2017 |
Publicly Available Date | Mar 9, 2017 |
Journal | Nature Communications |
Electronic ISSN | 2041-1723 |
Publisher | Nature Publishing Group |
Peer Reviewed | Peer Reviewed |
Volume | 8 |
Article Number | 14137 |
DOI | https://doi.org/10.1038/ncomms14137 |
Public URL | https://nottingham-repository.worktribe.com/output/847758 |
Publisher URL | http://www.nature.com/articles/ncomms14137 |
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Copyright Statement
Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0
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