Cyclometalated platinum complexes have been synthesized with tridendate C^N^N-type ligands and characterized by NMR spectroscopy and X-ray diffraction (XRD).  Regioselective addition of C-X bonds versus C-H bonds was examined.  Exclusively six or exclusively five-membered platinacycles are formed depending on ligand architecture.  Two platinum(IV) species, formed by oxidative addition of C-X, with the rare six-membered metalacycle, have been characterized by X-ray diffraction.  The C^N^N ligand adopts the mer configuration while the three carbon donors adopt the fac geometry. Regarding the regioselectivity, C-X is activated exclusively over C-H and sp2 C-H bonds exclusively over sp3 C-H bonds. The reductive elimination reactions were studied in order to examine whether C-C couplings from the platinum center were possible.

Regioselective synthesis of six-membered and five-membered cyclometalated platinum complexes

248th National Meeting (2014)

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