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

Author

Listed:
  • Matthew Gregson

    (School of Chemistry, The University of Manchester)

  • Erli Lu

    (School of Chemistry, The University of Manchester)

  • David P. Mills

    (School of Chemistry, The University of Manchester)

  • Floriana Tuna

    (EPSRC National UK EPR Facility, School of Chemistry and Photon Science Institute, The University of Manchester)

  • Eric J. L. McInnes

    (EPSRC National UK EPR Facility, School of Chemistry and Photon Science Institute, The University of Manchester)

  • Christoph Hennig

    (Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology
    Bautzner Landstrasse 400
    The Rossendorf Beamline, ESRF)

  • Andreas C. Scheinost

    (Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology
    Bautzner Landstrasse 400
    The Rossendorf Beamline, ESRF)

  • Jonathan McMaster

    (School of Chemistry, University of Nottingham)

  • William Lewis

    (School of Chemistry, University of Nottingham)

  • Alexander J. Blake

    (School of Chemistry, University of Nottingham)

  • Andrew Kerridge

    (Lancaster University)

  • Stephen T. Liddle

    (School of Chemistry, The University of Manchester)

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.

Suggested Citation

  • Matthew Gregson & Erli Lu & David P. Mills & Floriana Tuna & Eric J. L. McInnes & Christoph Hennig & Andreas C. Scheinost & Jonathan McMaster & William Lewis & Alexander J. Blake & Andrew Kerridge & S, 2017. "The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes," Nature Communications, Nature, vol. 8(1), pages 1-11, April.
    • Handle: RePEc:nat:natcom:v:8:y:2017:i:1:d:10.1038_ncomms14137
    DOI: 10.1038/ncomms14137
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    Cited by:

    1. Alyssa N. Gaiser & Cristian Celis-Barros & Frankie D. White & Maria J. Beltran-Leiva & Joseph M. Sperling & Sahan R. Salpage & Todd N. Poe & Daniela Gomez Martinez & Tian Jian & Nikki J. Wolford & Nat, 2021. "Creation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexes," Nature Communications, Nature, vol. 12(1), pages 1-9, December.

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