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

Gregson, Matthew and Lu, Erli and Mills, David and Tuna, Floriana and McInnes, Eric and Hennig, Cristoph and Scheinost, Andreas and McMaster, Jonathan and Lewis, William and Blake, Alexander and Kerridge, Andrew and Liddle, Stephen (2017) The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes. Nature Communications, 8. 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 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.

Item Type:
Journal Article
Journal or Publication Title:
Nature Communications
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/asjc/3100
Subjects:
ID Code:
83666
Deposited By:
Deposited On:
15 Dec 2016 15:30
Refereed?:
Yes
Published?:
Published
Last Modified:
29 Sep 2020 03:20