Tateyama Haruko, Boggiano Andrew C, Liao Can, Otte Kaitlyn S, Li Xiaosong, La Pierre Henry S
School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, United States.
Department of Chemistry, University of Washington, Seattle, Washington 98195, United States.
J Am Chem Soc. 2024 Apr 17;146(15):10268-10273. doi: 10.1021/jacs.4c01964. Epub 2024 Apr 2.
High-valent cerium complexes of alkyl and benzyl ligands are unprecedented due to the incompatibility of the typically highly oxidizing Ce 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--butyl imidophosphorane ligand, [NP(Bu)]. The Ce monoiodide complex, [CeI(NP(-butyl))] (), serves as a precursor to the alkyl and benzyl complexes, [Ce(Npt)(NP(-butyl))] () (Npt = neopentyl, CHC(CH)) and [Ce(Bn)(NP(-butyl))] () (Bn = benzyl, CHPh). The bonding and structure of these complexes are characterized by single-crystal XRD, NMR and UV-vis-NIR spectroscopy, cyclic voltammetry, and DFT studies.
由于典型的高氧化性铈离子与还原性烷基或苄基配体不相容，烷基和苄基配体的高价铈配合物是前所未有的。在此，我们报告了由三叔丁基亚氨基膦配体[NP(Bu)]支撑的首例四价铈烷基和苄基配合物的合成与分离。碘化铈单核配合物[CeI(NP( - 丁基))]（）用作烷基和苄基配合物[Ce(Npt)(NP( - 丁基))]（）（Npt = 新戊基，CHC(CH)）和[Ce(Bn)(NP( - 丁基))]（）（Bn = 苄基，CHPh）的前体。通过单晶XRD、NMR和UV - vis - NIR光谱、循环伏安法以及DFT研究对这些配合物的键合和结构进行了表征。
