Osme Bond: Geometric and Energetic Features in the Adducts between OsO<sub>4</sub> and Lewis Bases
Miriam Calabrese, Andrea Pizzi, Andrea Daolio, Roberta Beccaria, Cristina Lo Iacono, Steve Scheiner, Giuseppe Resnati
Abstract
Abstract Adducts between OsO 4 and Lewis bases exert a role in important oxidation processes such as epoxidation and dihydroxylation. It has been shown that the attractive interaction driving the formation of these adducts is a σ‐hole bond involving the metal as the electrophilic species; the term Osme Bond (OmB) was proposed for designating it. Here some new adducts between OsO 4 and various bases have been characterized through single crystal x‐ray diffraction (XRD) and computational studies (density functional theory, DFT), confirming the existence of a robust correlation between σ‐hole interaction energy and deformation of the tetrahedral geometry of OsO 4 . Also, some adducts formed by RuO 4 with nucleophiles were investigated computationally.