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


Ontology type: schema:ScholarlyArticle      Open Access: True


Article Info

DATE

2017-02-03

AUTHORS

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, Stephen T. Liddle

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. More... »

PAGES

14137

References to SciGraph publications

Identifiers

URI

http://scigraph.springernature.com/pub.10.1038/ncomms14137

DOI

http://dx.doi.org/10.1038/ncomms14137

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1083524744

PUBMED

https://www.ncbi.nlm.nih.gov/pubmed/28155857


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