The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes.
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.
School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Matthew
M
Gregson
School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Erli
E
Lu
School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK.
David P
DP
Mills
EPSRC National UK EPR Facility, School of Chemistry and Photon Science Institute, The University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Floriana
F
Tuna
EPSRC National UK EPR Facility, School of Chemistry and Photon Science Institute, The University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Eric J L
EJ
McInnes
Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, Bautzner Landstrasse 400, D-01314 Dresden, Germany.|The Rossendorf Beamline, ESRF, BP 220, F-38043 Grenoble, France.
Christoph
C
Hennig
Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, Bautzner Landstrasse 400, D-01314 Dresden, Germany.|The Rossendorf Beamline, ESRF, BP 220, F-38043 Grenoble, France.
Andreas C
AC
Scheinost
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
Jonathan
J
McMaster
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
William
W
Lewis
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
Alexander J
0000-0003-2257-8332
AJ
Blake
Department of Chemistry, Lancaster University, Lancaster LA1 4YB, UK.
Andrew
0000-0002-2876-1202
A
Kerridge
School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Stephen T
ST
Liddle