Reversible Grafting in Surface Organometallic Chemistry with a Late Transition‐Metal Amidinate Precursor

Abstract Supported catalysts are central to industrial catalytic processes. While traditional synthesis methods often yield poorly defined materials, thus complicating structural elucidation, Surface Organometallic Chemistry (SOMC) offers a solution, producing well‐defined structures. Recent advances in SOMC precursor development have shown that amidinate‐based complexes are a privileged class of precursors to generate supported metallic nanoparticles. In that context, this study investigates the grafting mechanism of a prototypical amidinate precursor, Ir(COD)(DIA) ( 1‐Ir ), onto SiO 2 . Unique to amidinate complexes, grafting is shown to occur without ligand release, creating a reversible covalent bond. Using tris( tert ‐butoxy)silanol as a molecular analogue for a silanol group on SiO 2 , the structure of the grafted species is elucidated by single X‐Ray diffraction, comparison of IR spectroscopy, and X‐Ray absorption spectroscopy (XAS) data. The reversibility of the reaction with O−H groups is demonstrated using variable‐temperature NMR spectroscopy, IR spectroscopy, and is supported by DFT calculations. Notably, we show that a partial degrafting is also possible at elevated temperatures under vacuum.