This work focused on the synthesis of tridentate anionic carbazolyl/bis(imine) (NNN) pincer complexes of platinum with the ultimate goal of generating a 3-coordinate unsaturated 14-electron platinum(II) complex. Pincer ligands are useful as they can stabilize extremely reactive transition metal complexes.1 However, previous studies of tridentate pincer complexes using ligands such as PNP or PONOP have demonstrated these pincer ligands are not suitable for the isolation of stable unsaturated platinum complexes with an open coordination site. Attempts to generate 3-coordinate species with PNP resulted in the heterolytic splitting of aromatic C-H bonds in solvents like benzene.2 The NNN ligand family is favored for its rigidity and resistance to oxidation.3 Abstraction of the triflate group from (NNN)PtOTf was explored in order to synthesize the three coordinate species. Adventitious water was observed to react with (NNN)PtOTf to form a water adduct which was characterized by multinuclear NMR and X-ray diffraction studies. Surprisingly, upon addition of triethylamine to react with residual triflic acid in the synthetic workup of (NNN)PtOTf, cyclometallation through intramolecular C-H activation of an ortho alkyl group of a mesityl sidearm was observed.(1) Ozerov, O.V., The Chemistry of Pincer Ligands; Elsevier B.V., Amsterdam, 2007 , 287-309(2) Ozerov, O.V. et al., Chem. Sci., 2013 , 4, 642-649(3) Ozerov, O.V. et al., Inorg. Chem., 2011 , 50 (8), 3673�3679

Synthesis of tridentate anionic carbazolyl/bis(imine) pincer complexes of platinum

247th National Meeting (2014)

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