Grace B Panetti1, Dumitru-Claudiu Sergentu2, Michael R Gau1, Patrick J Carroll1, Jochen Autschbach3, Patrick J Walsh4, Eric J Schelter5. 1. Roy and Diana Vagelos Laboratories Department of Chemistry, University of Pennsylvania, Philadelphia, PA, USA. 2. Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY, USA. 3. Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY, USA. jochena@buffalo.edu. 4. Roy and Diana Vagelos Laboratories Department of Chemistry, University of Pennsylvania, Philadelphia, PA, USA. pwalsh@sas.upenn.edu. 5. Roy and Diana Vagelos Laboratories Department of Chemistry, University of Pennsylvania, Philadelphia, PA, USA. schelter@sas.upenn.edu.
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.
The synn class="Chemical">thesis 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 demonstratethat SOC-driven deshielding is present for CeIV - Cipso13C{1H} resonances and not just for diamagnetic actinide compounds.
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