Crafting Versatile Modes of Pt(II) Complexes with Flexidentate Pyridyl‐β‐diketones: Synthesis, Structural Characterization, and Catalytic Behavior in Olefin Hydrosilylation

Abstract

Cycloplatinated complexes, with their high reactivity, combined with the capability to tailor ligands for specific catalytic processes, play a pivotal role in materials science and coordination chemistry, serving as versatile catalysts for applications in the organic synthesis of industrially relevant processes. In this report, we describe the synthesis and characterization of a new family of Pt(II) complexes based on three isomeric pyridyl‐β‐diketones diversified in terms of N‐atom location in the heterocyclic ring. By appropriate control of the reaction conditions, we were able to generate distinct coordination species, featuring ligands arranged as N,C(sp3)‐ and N,O‐chelates, as well as simple pyridyl‐N donors. Various analytical techniques, including X‐Ray diffraction, NMR spectroscopy and ESI‐MS spectrometry enabled the characterization of different coordination modes of the central atoms and unambiguously established the complex structures. Furthermore, all the Pt(II) coordination units have been found to be highly active and selective catalyst precursors in the hydrosilylation reactions within a broad scope of olefins with hydrosilanes.