The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

Matthew Gregson, Erli Lu, David P. Mills, Floriana Tuna, Eric J. L. McInnes, Christoph Hennig, Andreas C. Scheinost, Jonathan McMaster, William Lewis, Alexander J. Blake, Andrew Kerridge () and Stephen T. Liddle ()
Additional contact information
Matthew Gregson: School of Chemistry, The University of Manchester
Erli Lu: School of Chemistry, The University of Manchester
David P. Mills: School of Chemistry, The University of Manchester
Floriana Tuna: EPSRC National UK EPR Facility, School of Chemistry and Photon Science Institute, The University of Manchester
Eric J. L. McInnes: EPSRC National UK EPR Facility, School of Chemistry and Photon Science Institute, The University of Manchester
Christoph Hennig: Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology
Andreas C. Scheinost: Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology
Jonathan McMaster: School of Chemistry, University of Nottingham
William Lewis: School of Chemistry, University of Nottingham
Alexander J. Blake: School of Chemistry, University of Nottingham
Andrew Kerridge: Lancaster University
Stephen T. Liddle: School of Chemistry, The University of Manchester

Nature Communications, 2017, vol. 8, issue 1, 1-11

Abstract: Abstract 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.

Date: 2017
References: Add references at CitEc
Citations: View citations in EconPapers (1)

Downloads: (external link)
https://www.nature.com/articles/ncomms14137 Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:8:y:2017:i:1:d:10.1038_ncomms14137

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/ncomms14137

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().