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Characterization of a Paramagnetic, Mononuclear Pt (II)-Alkyl Complex Intermediate in Carbon-Halogen Bond Coupling Reaction


Orestes Rivada-Wheelaghan, Manuel A. Ortuño, Josefina Díez, Sergio García-Garrido, Celia Maya, Agustí Lledós, Salvador Conejero J. Am. Chem. Soc. 2012, Vol. 134, 15261–15264

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.