(BB)-Carboryne Complex of Ruthenium: Synthesis by Double B–H Activation at a Single Metal Center

The first example of a transition metal (BB)-carboryne complex containing two boron atoms of the icosahedral cage connected to a single exohedral metal center (POBBOP)­Ru­(CO)₂ (POBBOP = 1,7-OP­(i-Pr)₂-2,6-dehydro-m-carborane) was synthesized by double B–H activation within the strained m-carboranyl pincer framework. Theoretical calculations revealed that the unique three-membered (BB)>Ru metalacycle is formed by two bent B–Ru σ-bonds with the concomitant increase of the bond order between the two metalated boron atoms. The reactivity of the highly strained electron-rich (BB)-carboryne fragment with small molecules was probed by reactions with electrophiles. The carboryne–carboranyl transformations reported herein represent a new mode of cooperative metal–ligand reactivity of boron-based complexes.