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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 ¼ 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 ¼ Cu and Ag, or the pairs of two-center-two electron B–Au and Au–Ru interactions for M ¼ Au. These transformations comprise the first synthetic route to exohedral coinage metal boryl complexes of icosahedral closo-{C2B10} clusters, which feature short Cu–B (2.029(2) A) and Ag ˚ –B (2.182(3) A) bonds and the shortest Au ˚ –B bond (2.027(2) A) 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.

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© The Royal Society of Chemistry 2018

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APA Citation

Eleazer, B. J., Smith, M. D., Popov, A. A., & Peryshkov, D. V. (2018). Expansion of the (BB)Ru metallacycle with coinage metal cations: formation of B–M–Ru–B (M = Cu, Ag, Au) dimetalacyclodiboryls. Chemical Science, 9(9), 2601–2608.