Oxidative Reactivity of (N2S2)PdRX Complexes (R = Me, Cl; X = Me, Cl, Br): Involvement of Palladium(III) and Palladium(IV) Intermediates

A series of (N2S2)­PdRX complexes (N2S2 = 2,11-dithia[3.3]­(2,6)­pyridinophane; R = X = Me, <b>1</b>; R = Me, X = Cl, <b>2</b>; R = Me, X = Br, <b>3</b>; R = X = Cl, <b>4</b>) were synthesized, and their structural and electronic properties were investigated. X-ray crystal structures show that for the corresponding Pd­(II) complexes the N2S2 ligand adopts a κ² conformation, with the pyridine N donors binding in the equatorial plane. Cyclic voltammetry (CV) studies suggest that the Pd­(III) oxidation state is accessible at moderate redox potentials. In situ EPR, ESI-MS, UV–vis, and low-temperature electrochemical studies were employed to detect the formation of Pd­(III) species during the oxidation of Pd­(II) precursors. In addition, the [(N2S2)­Pd^IVMe₂]­(PF₆)₂ ([<b>1</b>²⁺]­(PF₆)₂) complex was isolated by oxidation of <b>1</b> with 2 equiv of FcPF₆, and its structural characterization reveals an octahedral Pd­(IV) center. The reversible Pd^IV/III redox couple for the Pd­(IV) species supports the observed formation of the Pd­(III)–dimethyl species upon chemical reduction of <b>1</b>²⁺. In addition, reactivity studies reveal ethane, MeCl, and MeBr elimination upon one-electron oxidation of <b>1</b> (as well as the one-electron reduction of <b>1</b>²⁺), <b>2</b>, and <b>3</b>, respectively. Mechanistic studies suggest the initial formation of a Pd­(III) species, followed by methyl group transfer/disproportionation and subsequent reductive elimination from a Pd­(IV) intermediate, although a halogen radical pathway cannot be completely excluded during C–halide bond formation. Interestingly, computational results suggest that the N2S2 ligand stabilizes to a greater extent the Pd­(IV) vs the Pd­(III) oxidation state, likely due to steric rather than electronic effects