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Addition of Br2 or I2 to 14-electron, cationic Pt(II)-alkyl complexes led to the formation of the corresponding carbon-halogen Pt(II) coupling products. Low temperature experiments with Br2 allowed us to isolate and characterize crystallographically a very unusual mononuclear, paramagnetic Pt(III)-alkyl intermediate with a seesaw structure that can be further oxidized to a transient Pt(IV) species before reductive carbon-halogen coupling reaction takes place.

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