Tetravalent Cerium Alkyl and Benzyl Complexes

Haruko Tateyama; Andrew C Boggiano; Can Liao; Kaitlyn S Otte; Xiaosong Li; Henry S La Pierre

doi:10.1021/jacs.4c01964

Tetravalent Cerium Alkyl and Benzyl Complexes

J Am Chem Soc. 2024 Apr 17;146(15):10268-10273. doi: 10.1021/jacs.4c01964. Epub 2024 Apr 2.

Authors

Haruko Tateyama¹, Andrew C Boggiano¹, Can Liao², Kaitlyn S Otte¹, Xiaosong Li², Henry S La Pierre^{1

3

4}

Affiliations

¹ School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, United States.
² Department of Chemistry, University of Washington, Seattle, Washington 98195, United States.
³ Nuclear and Radiological Engineering and Medical Physics Program, School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, United States.
⁴ Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352, United States.

Abstract

High-valent cerium complexes of alkyl and benzyl ligands are unprecedented due to the incompatibility of the typically highly oxidizing Ce⁴⁺ 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(^tBu)₃]^1-. The Ce⁴⁺ monoiodide complex, [Ce⁴⁺I(NP(tert-butyl)₃)₃] (1-CeI), serves as a precursor to the alkyl and benzyl complexes, [Ce⁴⁺(Npt)(NP(tert-butyl)₃)₃] (2-CeNpt) (Npt = neopentyl, CH₂C(CH₃)₃) and [Ce⁴⁺(Bn)(NP(tert-butyl)₃)₃] (2-CeBn) (Bn = benzyl, CH₂Ph). The bonding and structure of these complexes are characterized by single-crystal XRD, NMR and UV-vis-NIR spectroscopy, cyclic voltammetry, and DFT studies.