The field of platinum chemistry is ubiquitous in the research of anticancer drugs and new OLED materials. Within the vast library of existing compounds, the majority of work focuses on complexes in the +2 and +4 oxidation states, with comparatively few examples of PtIII complexes reported without bridging ligands. PtIII complexes with metal-metal bonding can be made by mild oxidation of PtII complexes having bis(phenylpyridine) ligands. Here, we report the synthesis and characterization of two new PtII complexes bearing tetradentate N-bridged bis(phenylpyridine) ligands with N^C*C^N and C^N*N^C coordinating atoms. Through chemical oxidation with PhICl2 and N-chlorosuccinimide, we obtained four new complexes containing PtIV and PtIII centres. The dynamics of the PtIII complexes were explored by variable-temperature NMR studies and showed surprisingly free rotation of the appended N-aryl group. This work uncovers the importance of the destabilizing nature of the bulky N-aryl group on intermetallic bonds, and sheds light on how the molecular rotation observed in the PtIII compounds could inspire new molecular rotors driven by intermetallic bonds.
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