Platinum Group Organometallics Based on "Pincer" Complexes: Sensors, Switches, and Catalysts In memory of Prof. Dr. Luigi M. Venanzi and his pioneering work in organometallic chemistry, particularly in PCP pincer chemistry.

Since the first reports in the late 1970s on transition metal complexes containing pincer-type ligands-named after the particular coordination mode of these ligands-these systems have attracted increasing interest owing to the unusual properties of the metal centers imparted by the pincer ligand. Typically, such a ligand comprises an anionic aryl ring which is ortho,ortho-disubstituted with heteroatom substituents, for example, CH(2)NR(2), CH(2)PR(2) or CH(2)SR, which generally coordinate to the metal center, and therefore support the M-C sigma bond. This commonly results in a terdentate and meridional coordination mode consisting of two metallacycles which share the M-C bond. Detailed studies of the formation and the properties of a large variety of pincers containing platinum group metal complexes have provided direct access to both a fundamental understanding of a variety of reactions in organometallic chemistry and to a range of new applications of these complexes. The discovery of alkane dehydrogenation catalysts, the mechanistic elucidation of fundamental transformations (for example, C-C bond activation), the construction of the first metallodendrimers for sustainable homogeneous catalysis, and the engineering of crystalline switches for materials processing represent only a few of the many highlights which have emanated from these numerous investigations. This review discusses the synthetic methodologies that are currently available for the preparation of platinum group metal complexes containing pincer ligands and especially emphasizes different applications that have been realized in materials science such as the development and engineering of sensors, switches, and catalysts.