Identification of a uranium–rhodium triple bond in a heterometallic cluster

Abstract

The chemistry of d-block metal–metal multiple bonds has been extensively investigated in the past 5 decades. However, the synthesis and characterization of species with f-block metal–metal multiple bonds are significantly more challenging and such species remain extremely rare. Here, we report the identification of a uranium–rhodium triple bond in a heterometallic cluster, which was synthesized under routine conditions. The uranium–rhodium triple-bond length of 2.31 Å in this cluster is only 3% longer than the sum of the covalent triple-bond radii of uranium and rhodium (2.24 Å). Computational studies reveal that the nature of this uranium–rhodium triple bond is 1 covalent bond with 2 rhodium-to-uranium dative bonds. This heterometallic cluster represents a species with f-block metal–metal triple bond structurally authenticated by X-ray diffraction. These studies not only demonstrate the authenticity of the uranium–metal triple bond, but also provide a possibility for the synthesis of other f-block metal–metal multiple bonds. We expect that this work may further our understanding of the bonding between uranium and transition metals, which may help to design new d-f heterometallic catalysts with uranium–metal bonds for small-molecule activation and to promote the utilization of abundant depleted uranium resources.