Isolation and characterization of a covalent CeIV-Aryl complex with an anomalous 13C chemical shift

Grace B. Panetti, Dumitru-Claudiu Sergentu, Michael R. Gau, Patrick J. Carroll, Jochen Autschbach (), Patrick J. Walsh () and Eric J. Schelter ()
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Grace B. Panetti: University of Pennsylvania
Dumitru-Claudiu Sergentu: University at Buffalo, State University of New York
Michael R. Gau: University of Pennsylvania
Patrick J. Carroll: University of Pennsylvania
Jochen Autschbach: University at Buffalo, State University of New York
Patrick J. Walsh: University of Pennsylvania
Eric J. Schelter: University of Pennsylvania

Nature Communications, 2021, vol. 12, issue 1, 1-7

Abstract: Abstract The synthesis of bona fide organometallic CeIV complexes is a formidable challenge given the typically oxidizing properties of the CeIV cation and reducing tendencies of carbanions. Herein, we report a pair of compounds comprising a CeIV − Caryl bond [Li(THF)4][CeIV(κ2-ortho-oxa)(MBP)2] (3-THF) and [Li(DME)3][CeIV(κ2-ortho-oxa)(MBP)2] (3-DME), ortho-oxa = dihydro-dimethyl-2-[4-(trifluoromethyl)phenyl]-oxazolide, MBP2– = 2,2′-methylenebis(6-tert-butyl-4-methylphenolate), which exhibit CeIV − Caryl bond lengths of 2.571(7) – 2.5806(19) Å and strongly-deshielded, CeIV − Cipso 13C{1H} NMR resonances at 255.6 ppm. Computational analyses reveal the Ce contribution to the CeIV − Caryl bond of 3-THF is ~12%, indicating appreciable metal-ligand covalency. Computations also reproduce the characteristic 13C{1H} resonance, and show a strong influence from spin-orbit coupling (SOC) effects on the chemical shift. The results demonstrate that SOC-driven deshielding is present for CeIV − Cipso 13C{1H} resonances and not just for diamagnetic actinide compounds.

Date: 2021
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DOI: 10.1038/s41467-021-21766-4

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