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

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  • Matthew Gregson
  • Erli Lu
  • David Mills
  • Floriana Tuna
  • Eric McInnes
  • Cristoph Hennig
  • Andreas Scheinost
  • Jonathan McMaster
  • William Lewis
  • Alexander Blake
  • Andrew Kerridge
  • Stephen Liddle
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Article number14137
<mark>Journal publication date</mark>3/02/2017
<mark>Journal</mark>Nature Communications
Volume8
Number of pages11
Publication statusPublished
Original languageEnglish

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.