Direct Detection\nof Pt(IV) Phenyl Complexes upon Intermolecular\nOxidative Addition of Aryl Halides and Selective Csp<sup>3</sup>–I\nversus Csp<sup>2</sup>–Csp<sup>3</sup> and Csp<sup>3</sup>–Csp<su

Reaction of a chelating N-heterocyclic carbene Pt(II)\ndimethyl\ncomplex with phenyl iodide and excess KI results in the direct detection\nof a Pt(IV) phenyl intermediate by <sup>1</sup>H NMR spectroscopy.\nThis finding provides experimental evidence that the reaction between\nPt(II) dimethyl complexes and aryl halides proceeds via a concerted\noxidative addition (OA) mechanism. Additionally, we report on the\nselective reductive elimination (RE) of Csp<sup>3</sup>–I vs\nCsp<sup>2</sup>–Csp<sup>3</sup> and Csp<sup>3</sup>–Csp<sup>3</sup> bonds. Lastly, OA, different RE pathways, and reactivity\nof different isomers were investigated by computational methods that\nare consistent with experimental observations. We believe that these\nresults have important implications for the development of new Pt-catalyzed\ntransformations.