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

Research output: Contribution to journalArticle

  • External authors:
  • Matthew Gregson
  • Erli Lu
  • Floriana Tuna
  • Christoph Hennig
  • Andreas C Scheinost
  • Jonathan McMaster
  • William Lewis
  • Alexander J. Blake
  • Andrew Kerridge

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.

Bibliographical metadata

Original languageEnglish
Article number14137
JournalNature communications
Volume8
Early online date3 Feb 2017
DOIs
StatePublished - 2017