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

Gregson, Matthew; Lu, Erli; Mills, David P.; Tuna, Floriana; McInnes, Eric J.L.; Hennig, Christoph; Scheinost, Andreas C.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Kerridge, Andrew; Liddle, Stephen T.

Abstract

© 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.

Citation

Gregson, M., Lu, E., Mills, D. P., Tuna, F., McInnes, E. J., Hennig, C., Scheinost, A. C., McMaster, J., Lewis, W., Blake, A. J., Kerridge, A., & Liddle, S. T. (2017). The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes. Nature Communications, 8, Article 14137. https://doi.org/10.1038/ncomms14137

• Journal Article Type: Article
• Acceptance Date: Dec 2, 2016
• Online Publication Date: Feb 3, 2017
• Publication Date: Feb 3, 2017
• Deposit Date: Mar 9, 2017
• Publicly Available Date: Mar 9, 2017
• Journal: Nature Communications
• Electronic ISSN: 2041-1723
• Publisher: Nature Publishing Group
• Peer Reviewed: Peer Reviewed
• Volume: 8
• Article Number: 14137
• DOI: https://doi.org/10.1038/ncomms14137
• Public URL: https://nottingham-repository.worktribe.com/output/847758
• Publisher URL: http://www.nature.com/articles/ncomms14137
• Contract Date: Mar 9, 2017