期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2019
卷号：116
期号：36
页码：17654-17658
DOI：10.1073/pnas.1904895116
出版社：The National Academy of Sciences of the United States of America
摘要：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..
关键词：chemical bonding ; metal–metal bond ; uranium–metal multiple bond ; heterometallic cluster ; DFT
