Silica‐Supported Mononuclear Methyl‐Platinum Complexes Stabilized by Trimethylphosphine—Synthesis, Structure, and Reactions Under Reducing Conditions

The chemistry of single‐site platinum surface complexes with phosphine ligands is rarely understood, in contrast to its well‐known chemistry in solution. This report describes the synthesis of a supported bis(phosphine)methylplatinum(II) complex on silicon dioxide (PtMe(PMe 3 ) 2 /SiO 2 ) and its reactivity with carbon monoxide, hydrogen, and under inert gas. The parent compound and reaction intermediates are characterized by IR‐, solid‐state NMR, and X‐ray absorption spectroscopy. The sterically non‐demanding monodentate phosphine ligands stabilize the platinum centers, allowing the formation of several isolated trans complexes on silica. One of them is a platinum hydride that effectively catalyzes the isomerization of 1‐hexene. The stabilization of the molecular hydride contrasts with the reactivity of known supported platinum methyl complexes, such as PtMe(cod)/SiO 2 , which tend to form supported platinum nanoparticles under the applied mild conditions.