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

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.

SUBMITTER: Panetti GB 

PROVIDER: S-EPMC7969749 | biostudies-literature | 2021 Mar

REPOSITORIES: biostudies-literature

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Isolation and characterization of a covalent Ce<sup>IV</sup>-Aryl complex with an anomalous <sup>13</sup>C chemical shift.

Panetti Grace B GB   Sergentu Dumitru-Claudiu DC   Gau Michael R MR   Carroll Patrick J PJ   Autschbach Jochen J   Walsh Patrick J PJ   Schelter Eric J EJ  

Nature communications 20210317 1

The synthesis of bona fide organometallic Ce<sup>IV</sup> complexes is a formidable challenge given the typically oxidizing properties of the Ce<sup>IV</sup> cation and reducing tendencies of carbanions. Herein, we report a pair of compounds comprising a Ce<sup>IV</sup> - C<sub>aryl</sub> bond [Li(THF)<sub>4</sub>][Ce<sup>IV</sup>(κ<sup>2</sup>-ortho-oxa)(MBP)<sub>2</sub>] (3-THF) and [Li(DME)<sub>3</sub>][Ce<sup>IV</sup>(κ<sup>2</sup>-ortho-oxa)(MBP)<sub>2</sub>] (3-DME), ortho-oxa = dihydro-di  ...[more]

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