title: (BB)-Carboryne Complex of Ruthenium: Synthesis by Double B-H Activation at a Single Metal Center.
abstract: 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.
authors.affiliation: Department of Chemistry and Biochemistry, University of South Carolina , 631 Sumter Street, Columbia, South Carolina 29208, United States.
authors.forename: Bennett J
authors.initials: BJ
authors.lastname: Eleazer
authors.affiliation: Department of Chemistry and Biochemistry, University of South Carolina , 631 Sumter Street, Columbia, South Carolina 29208, United States.
authors.forename: Mark D
authors.initials: MD
authors.lastname: Smith
authors.affiliation: Leibniz Institute for Solid State and Materials Research , Helmholtzstrasse 20, 01069 Dresden, Germany.
authors.forename: Alexey A
authors.initials: AA
authors.lastname: Popov
authors.affiliation: Department of Chemistry and Biochemistry, University of South Carolina , 631 Sumter Street, Columbia, South Carolina 29208, United States.
authors.forename: Dmitry V
authors.initials: DV
authors.lastname: Peryshkov