Silica-supported Z-selective Ru olefin metathesis catalysts

[Display omitted] •Synthesis of a mesostructured hybrid silica material containing bulky thiol groups.•Immobilization of Ru-alkylidene complexes via a chlorine to thiol exchange.•Development of the first Z-selective olefin metathesis catalysts.•Activity and stereoselectivity comparable to that obtained with the homogeneous versions. Recently reported thiolate-coordinated ruthenium alkylidene complexes show promise in Z-selective and stereoretentive olefin metathesis reactions. Herein we describe the immobilization of three Ru complexes containing a bulky aryl thiolate on mesostructured silica via surface organometallic chemistry. The applied methodology gives isolated catalytic sites homogeneously distributed on the silica surface. The catalytic results with two model substrates show comparable Z-selectivities to those of the homogeneous counterparts.