Actinide acetylide complexes are of interest for their ability to reveal electronic structure information about the actinides and their unique reactivity. Herein, I describe the synthesis and characterization of several actinide parent acetylide complexes, including [An(C≡CH)(NR2)3] and [Na(TMEDA)][An(C≡CH)2(NR2)3] (An = U, Th; R = SiMe3). Analysis of the Th analogues by 13C NMR spectroscopy reveals downfield chemical shifts of the a-carbon resonances, indicative of 5f orbital participation in the Th-C bond. Additionally, thermolysis of [An(C≡CH)(NR2)3] (An = U, Th) results in the formation of the bimetallic dicarbide complexes, [{An(NR2)3}2(μ,η1:η1-C2)], along with free acetylene. Our attempts to reduce the acetylide ligands will also be described.

Synthesis and characterization of actinide parent acetylide complexes

ACS Fall 2021

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