Expansion of the (BB) 〉metallacycle with coinage metal cations: formation of B–M–Ru–B (M = Cu, Ag, Au) dimetalacyclodiboryls

In this work, we introduce a novel approach for the selective assembly of heterometallic complexes by unprecedented coordination of coinage metal cations to strained single ruthenium–boron bonds on a surface of icosahedral boron clusters. M(i) cations (M = Cu, Ag, and Au) insert into B–Ru bonds of the (BB)–carboryne complex of ruthenium with the formation of four-membered B–M–Ru–B metalacycles. Results of theoretical calculations suggest that bonding within these metalacycles can be best described as unusual three-center-two-electron B–M···Ru interactions that are isolobal to B–H···Ru borane coordination for M = Cu and Ag, or the pairs of two-center-two electron B–Au and Au–Ru interactions for M = Au. These transformations comprise the first synthetic route to exohedral coinage metal boryl complexes of icosahedral closo-{C(2)B(10)} clusters, which feature short Cu–B (2.029(2) Å) and Ag–B (2.182(3) Å) bonds and the shortest Au–B bond (2.027(2) Å) reported to date. The reported heterometallic complexes contain Cu(i) and Au(i) centers in uncharacteristic square-planar coordination environments. These findings pave the way to rational construction of a broader class of multimetallic architectures featuring M–B bonds.