ACS AuthorChoiceEleazer, Bennett J.Smith, Mark D.Popov, Alexey A.Peryshkov, Dmitry V.2022-05-182022-05-182016https://oa.tib.eu/renate/handle/123456789/8996https://doi.org/10.34657/8034The 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.enghttps://pubs.acs.org/page/policy/authorchoice_termsofuse.html540BoronChemical activationMetalsPraseodymiumRuthenium compoundsTransition metalsBond orderingElectron-richElectrophilesHighly strainedMetal centersMetal ligandsSmall moleculesTheoretical calculationsRutheniumboroncarboryne complexelectrophilehydrogenruthenium complextransition elementunclassified drugchemical bondchemical structurecycloadditionelectronnucleophilicityultraviolet irradiationArticle