Selective hydroboration of terminal alkynes catalyzed by heterometallic clusters with uranium metal triple bonds

Due to their fascinating structures and heterometallic synergistic effects in catalysis, heterometallic clusters with metal-metal (M-M) bonds have attracted the interest of chemists for decades. However, understanding of the chemistry of M-M bonds that involve f-block elements, such as uranium, is significantly less developed compared with that of the d-block transition metals, and catalysis by heterometallic clusters with U-M bonds has not been realized to date. Here, we report a set of heterometallic clusters that feature U M (M = Fe, Co) triple bonds. The cluster with two U Co triple bonds exhibits excellent catalytic activity for the hydroboration of alkynes under mild conditions, producing alpha-vinylboronates with good yields and regioselectivity. These heterometallic clusters represent the rare structurally authenticated example of multiple bonding between f-block elements and transition metals. Theoretical studies reveal high bond orders (up to 2.93) and a significant degree of covalency in these U M triple bonds.