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(PMe3)2/SiO2) 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)/SiO2, which tend to form supported platinum nanoparticles under the applied mild conditions.