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- W3136797793 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 - Cipso13C{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 - Cipso13C{1H} resonances and not just for diamagnetic actinide compounds." @default.
- W3136797793 created "2021-03-29" @default.
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- W3136797793 date "2021-03-17" @default.
- W3136797793 modified "2023-10-11" @default.
- W3136797793 title "Isolation and characterization of a covalent CeIV-Aryl complex with an anomalous 13C chemical shift" @default.
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- W3136797793 doi "https://doi.org/10.1038/s41467-021-21766-4" @default.
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