New Aspects of Ruthenium-Mediated Polyhedral Contraction of Monocarbollides

It has been shown that the interaction of tris(triphenylphosphine)ruthenium dichloride RuCl2(PPh3)3 (1) with 10-vertex monocarborane [6-Ph-nido-6-CB9H11]−[Et4N]+ (2) under mild thermolysis conditions is not selective due to the undesired coordination of ruthenium to a phenyl substituent in the carborane and phosphine ligands, giving the series of new classical and non-classical metallacarborane complexes. In contrast, the reaction of 1 and monocarborane [arachno-6-CB9H14]−[Et4N]+ (3) proceeds more selectively with the formation of the only one product, a isocloso-structured metallacarborane. The structures of two ruthenacarboranes were resolved by X-ray diffraction. © 2022 by the authors.