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

Gregson, Matthew and Lu, Erli and Mills, David P. and Tuna, Floriana and McInnes, Eric J.L. and Hennig, Christoph and Scheinost, Andreas C. and McMaster, Jonathan and Lewis, William and Blake, Alexander J. and Kerridge, Andrew and Liddle, Stephen T. (2017) The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes. Nature Communications, 8 . p. 14137. ISSN 2041-1723

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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 inversetrans-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 C¼M¼C 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.

Item Type: Article
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Chemistry
Identification Number: 10.1038/ncomms14137
Depositing User: Bramwell, Roseanna
Date Deposited: 09 Mar 2017 14:12
Last Modified: 09 Mar 2017 14:17
URI: http://eprints.nottingham.ac.uk/id/eprint/41181

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