USc₂C₂ and USc₂NC Clusters with U–C Triple Bond Character Stabilized Inside Fullerene Cages

The chemistry of f-block metal–carbon multiple bonds is underdeveloped compared to well-established carbene complexes of the d-block transition metals. Herein, we report two new actinide-rare earth mixed metal carbides and nitrogen carbide cluster fullerenes, USc2C2@D5h(6)-C80 and USc2NC@D5h(6)-C80, which contain U–C bonds with triple bond character and were successfully synthesized and characterized by mass spectrometry, UV–vis–NIR spectroscopy, Fourier transform infrared spectroscopy, single crystal X-ray diffraction, and DFT calculations. Crystallographic studies show that the two previously unreported clusters, USc2C2 and USc2NC, are stabilized in the D5h(6)-C80 carbon cage and adopt unique trifoliate configurations, in which C2/NC units are almost vertically inserted into the plane defined by the U and two Sc atoms. Combined experimental and theoretical studies further reveal the bonding structure of USc2C2 and USc2NC, which contain C═U(VI)═C and C═U(V)═N bonding motifs. The electronic structures of the two compounds are determined as U6+(Sc2)6+(C4–)2@D5h(6)-C804– and U5+(Sc2)6+(N)3–(C)4–@D5h(6)-C804–, respectively. Quantum-chemical studies confirm that the U–C bonds in both molecules show unprecedented multicenter triple-bond character. The discovery of this unique U–C multiple bond offers a deeper understanding of the fundamentals of uranium chemistry.