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Tetravalent Cerium Alkyl and Benzyl Complexes.

Authors :: Tateyama H
Boggiano AC
Liao C
Otte KS
Li X
La Pierre HS
Source :: Journal of the American Chemical Society [J Am Chem Soc] 2024 Apr 17; Vol. 146 (15), pp. 10268-10273. Date of Electronic Publication: 2024 Apr 02.
Publication Year :: 2024
Abstract: High-valent cerium complexes of alkyl and benzyl ligands are unprecedented due to the incompatibility of the typically highly oxidizing Ce <superscript>4+</superscript> ion and the reducing alkyl or benzyl ligand. Herein we report the synthesis and isolation of the first tetravalent cerium alkyl and benzyl complexes supported by the tri- tert -butyl imidophosphorane ligand, [NP( <superscript>t</superscript> Bu) <subscript>3</subscript> ] <superscript>1-</superscript> . The Ce <superscript>4+</superscript> monoiodide complex, [Ce <superscript>4+</superscript> I(NP( tert -butyl) <subscript>3</subscript> ) <subscript>3</subscript> ] ( 1-CeI ), serves as a precursor to the alkyl and benzyl complexes, [Ce <superscript>4+</superscript> (Npt)(NP( tert -butyl) <subscript>3</subscript> ) <subscript>3</subscript> ] ( 2-CeNpt ) (Npt = neopentyl, CH <subscript>2</subscript> C(CH <subscript>3</subscript> ) <subscript>3</subscript> ) and [Ce <superscript>4+</superscript> (Bn)(NP( tert -butyl) <subscript>3</subscript> ) <subscript>3</subscript> ] ( 2-CeBn ) (Bn = benzyl, CH <subscript>2</subscript> Ph). The bonding and structure of these complexes are characterized by single-crystal XRD, NMR and UV-vis-NIR spectroscopy, cyclic voltammetry, and DFT studies.