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Lookup NU author(s): Dr Erli Lu,
Dr Stephen Liddle
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
© 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.
Author(s): Gregson M, Lu E, Mills DP, Tuna F, McInnes EJL, Hennig C, Scheinost AC, McMaster J, Lewis W, Blake AJ, Kerridge A, Liddle ST
Publication type: Article
Publication status: Published
Journal: Nature Communications
Online publication date: 03/02/2017
Acceptance date: 02/12/2016
Date deposited: 03/10/2019
ISSN (electronic): 2041-1723
Publisher: Nature Publishing Group
PubMed id: 28155857
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