Electron Transfer Induced CS Bond Cleavage in Rhenium and Technetium Thioether Complexes: Structural and Chemical Evidence for π Back‐Donation to CS σ^* Orbitals

Abstract

The trends in carbon‐sulfur bond length for complexes of 1,4,7‐trithiacyclononane (9S3) provide compelling evidence that CS σ * orbitals accept π‐electron density from the metal. As the metal d‐orbital energy and occupancy increase, this leads ultimately to cleavage of the CS bonds with concomitant release of ethene in the Re and Tc complexes [Eq. (a)]. equation image