NDLI: Emergence of comparable covalency in isostructural cerium(iv)– and uranium(iv)

Content Provider	Royal Society of Chemistry (RSC)
Author	Gregson, Matthew Liddle, Stephen T. Hennig, Christoph Lewis, William McMaster, Jonathan Blake, Alexander J. Tuna, Floriana Lu, Erli McInnes, Eric J. L. Scheinost, Andreas C. Kerridge, Andrew
Copyright Year	2016
Abstract	We report comparable levels of covalency in cerium– and uranium–carbon multiple bonds in the iso-structural carbene complexes [M(BIPMTMS)(ODipp)2] [M = Ce (1), U (2), Th (3); BIPMTMS = C(PPh2NSiMe3)2; Dipp = C6H3-2,6-iPr2] whereas for M = Th the MC bond interaction is much more ionic. On the basis of single crystal X-ray diffraction, NMR, IR, EPR, and XANES spectroscopies, and SQUID magnetometry complexes 1–3 are confirmed formally as bona fide metal(IV) complexes. In order to avoid the deficiencies of orbital-based theoretical analysis approaches we probed the bonding of 1–3via analysis of RASSCF- and CASSCF-derived densities that explicitly treats the orbital energy near-degeneracy and overlap contributions to covalency. For these complexes similar levels of covalency are found for cerium(IV) and uranium(IV), whereas thorium(IV) is found to be more ionic, and this trend is independently found in all computational methods employed. The computationally determined trends in covalency of these systems of Ce ∼ U > Th are also reproduced in experimental exchange reactions of 1–3 with MCl4 salts where 1 and 2 do not exchange with ThCl4, but 3 does exchange with MCl4 (M = Ce, U) and 1 and 2 react with UCl4 and CeCl4, respectively, to establish equilibria. This study therefore provides complementary theoretical and experimental evidence that contrasts to the accepted description that generally lanthanide–ligand bonding in non-zero oxidation state complexes is overwhelmingly ionic but that of uranium is more covalent.
Starting Page	3286
Ending Page	3297
Page Count	12
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	7
Issue Number	5
Journal	Chemical Science
DOI	10.1039/c6sc00278a
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	X-ray absorption near edge structure FIDE SQUID EPR Cerium Magnetometer Compact Cassette X-ray crystallography Carbene Uranium Covalent bond Nuclear magnetic resonance Thorium
Content Type	Text
Resource Type	Article
Subject	Chemistry

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