Convenient Route to Fischer-Type Carbene Ruthenium Complexes: Highly Selective Catalysts for Ring Opening/Cross-Metathesis of Norbornene Derivatives

The Fischer-type ruthenium carbene complexes RuCl 2 { C(H)ER}(PCy 3 ) 2 (ER = SPh ( 1a ), SC 6 H 4 Me- p ( 1b ), SC 6 H 4 Cl- p ( 1c ), SC 6 H 4 OMe- p ( 1d ), SePh ( 1e )) have been prepared by the reactions of Ru( p -cymene)(cod), PCy 3, and the corresponding dichloromethyl chalcogenides (Cl 2 CHER) in 47−80% yields. The starting Ru( p -cymene)(cod) is readily synthesized in high yield from [RuCl 2 ( p -cymene)] 2 . The X-ray structures of 1b and 1e are reported. Complexes 1a and 1e serve as highly selective catalysts for ring opening/cross-metathesis of norbornene derivatives with vinyl chalcogenides.