DFT studies of isomerization in palladium(IV) chemistry and alkyl halide transfer from palladium(IV) to palladium(II)

DFT computation supports mechanistic proposals for alkyl halide transfer from Pd(IV) to Pd(II) occurring via bridging transition structures, and accounting for selectivity of benzyl over methyl transfer. Computation for isomers of Pd(IV) complexes is in agreement with observed preferences and provides five-coordinate transition structures for isomerization formed after halide dissociation.167