Anion-Dependent Switch in C-X Reductive Elimination Diastereoselectivity

Reaction of a complex Pt organometallic species with electrophilic halogen sources in the presence of X- ligands changes the mechanism of reductive elimination from a concerted reductive coupling type to an S(N)2 type reductive elimination. In the absence of the added X- ligand the reductive elimination is stereoretentive; in its presence, the process is stereoinvertive. This selectivity hinges on the reactivity of a key five-coordinate Pt(IV) intermediate with the X- ligand.