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

Abstract The synthesis of bona fide organometallic Ce IV complexes is a formidable challenge given the typically oxidizing properties of the Ce IV cation and reducing tendencies of carbanions. Herein, we report a pair of compounds comprising a Ce IV − C aryl bond [Li(THF) 4 ][Ce IV (κ 2 - ortho -oxa)(MBP) 2 ] ( 3-THF ) and [Li(DME) 3 ][Ce IV (κ 2 - ortho -oxa)(MBP) 2 ] ( 3-DME ), ortho -oxa = dihydro-dimethyl-2-[4-(trifluoromethyl)phenyl]-oxazolide, MBP 2– = 2,2′-methylenebis(6- tert -butyl-4-methylphenolate), which exhibit Ce IV − C aryl bond lengths of 2.571(7) – 2.5806(19) Å and strongly-deshielded, Ce IV − C ipso 13 C{ 1 H} NMR resonances at 255.6 ppm. Computational analyses reveal the Ce contribution to the Ce IV − C aryl bond of 3-THF is ~12%, indicating appreciable metal-ligand covalency. Computations also reproduce the characteristic 13 C{ 1 H} 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 Ce IV − C ipso 13 C{ 1 H} resonances and not just for diamagnetic actinide compounds.