Secondary interactions are demonstrated to direct the stability of well-defined Ru-NHC-based heterogeneous alkene metathesis catalysts. By providing key stabilization of the active sites, higher catalytic performance is achieved. Specifically, they can be described as interactions between the metal center (active site) and the surface functionality of the support, and they have been detected by surface-enhanced (1)H-(29)Si NMR spectroscopy of the ligand and (31)P solid-state NMR of the catalyst precursor. They are present only when the metal center is attached to the surface via a flexible linker (a propyl group), which allows the active site to either react with the substrate or relax, reversibly, to the surface, thus providing stability. In contrast, the use of a rigid linker (here mesitylphenyl) leads to a well-defined active site far away from the surface, stabilized only by a phosphine ligand which under reaction conditions leaves probably irreversibly, leading to faster decomposition and deactivation of the catalysts.
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