Synthetic routes to methyl(aryl)alkynylpalladium(IV) motifs are presented, together with studies of selectivity in carbon–carbon coupling by reductive elimination from PdIV centres. The iodonium reagents IPh(C
CR)(OTf) (R = SiMe3, But, OTf = O3SCF3) oxidise PdIIMe(p-Tol)(L2) (1–3) [L2 = 1,2-bis(dimethylphosphino)ethane (dmpe) (1), 2,2′-bipyridine (bpy) (2), 1,10-phenanthroline (phen) (3)] in acetone-d6 or toluene-d9 at −80 °C to form complexes PdIV(OTf)Me(p-Tol)(C
CR)(L2) [R = SiMe3, L2 = dmpe (4), bpy (5), phen (6); R = But, L2 = dmpe (7), bpy (8), phen (9)] which reductively eliminate predominantly (>90%) p-Tol-C
CR above ∼−50 °C. NMR spectra show that isomeric mixtures are present for the PdIV complexes: three for dmpe complexes (4, 7), and two for bpy and phen complexes (5, 6, 8, 9), with reversible reduction in the number of isomers to two occurring between −80 °C and −60 °C observed for the dmpe complex 4 in toluene-d8. Kinetic data for reductive elimination from PdIV(OTf)Me(p-Tol)(C
CSiMe3)(dmpe) (4) yield similar activation parameters in acetone-d6 (66 ± 2 kJ mol−1, ΔH‡ 64 ± 2 kJ mol−1, ΔS‡ −67 ± 2 J K−1 mol−1) and toluene-d8 (Ea 68 ± 3 kJ mol−1, ΔH‡ 66 ± 3 kJ mol−1, ΔS‡ −74 ± 3 J K−1 mol−1). The reaction rate in acetone-d6 is unaffected by addition of sodium triflate, indicative of reductive elimination without prior dissociation of triflate. DFT computational studies at the B97-D level show that the energy difference between the three isomers of 4 is small (12.6 kJ mol−1), and is similar to the energy difference encompassing the six potential transition state structures from these isomers leading to three feasible C–C coupling products (13.0 kJ mol−1). The calculations are supportive of reductive elimination occurring directly from two of the three NMR observed isomers of 4, involving lower activation energies to form p-TolC
CSiMe3 and earlier transition states than for other products, and involving coupling of carbon atoms with higher s character of σ-bonds (sp2 for p-Tol, sp for C
C–SiMe3) to form the product with the strongest C–C bond energy of the potential coupling products. Reductive elimination occurs predominantly from the isomer with Me3SiC
C trans to OTf. Crystal structure analyses are presented for PdIIMe(p-Tol)(dmpe) (1), PdIIMe(p-Tol)(bpy) (2), and the acetonyl complex PdIIMe(CH2COMe)(bpy) (11).