Previously we reported the addition of ethylene and other alkenes to metal-stabilized thiyl radical complexes based on the bidentate ligand diphenylphosphinebenzenethiolate (Inorg. Chem., 2011  , 50, 9904�9914). Herein we report the reversible deprotonation of the ethylene addition product [Ru-1�C2H4]+  . Under basic conditions, the vinyl metallosulfonium derivative [Ru-1�C2H3]   is obtained in 96% yield. The product has been thoroughly characterized by 1H and 31P NMR, +ESI-MS, electrochemical methods, and X-ray crystallography. The addition of HCl or HBr reverses the reaction to regenerate [Ru-1�C2H4]+      The site of reversible deprotonation is selective as confirmed by experimental and density functional theory studies. Addition of   deuterium acids DCl/DBr to  [Ru-1�C2H3]   yields the a single mono-deuterated dithioether isomer [Ru-1�C2H3D]+   , which reacts selectively with base to regenerate the non-deuterated vinyl metallosulfonium complex.

Selective and reversible carbon-sulfur bond cleavage via deprotonation of a  Ru(II)-dithioether yields a stable vinyl metallosulfonium complex

244th National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.