Carbon–carbon and carbon–chlorine bond formation on reaction of iodine(III) reagents with the bis(alkynyl)palladium(II) motif, and structural chemistry of trans-Pd(Ctriple bond; length of mdashC-o-Tol)2(PMe2Ph)2] and trans-[PdCl(Ctriple bond; length of md

Trans-di(ortho-tolylethynyl)bis(dimethylphenylphosphine)palladium(II) reacts above −20 °C with the iodonium reagent IPhCl2 to give predominantly o-Tol–Ctriple bond; length of mdashC–Cl, above 15 °C with IPh2(OTf) (OTf = triflate) to give o-Tol–Ctriple bond; length of mdashC–Ph and (o-Tol–Ctriple bond; length of mdashC)2 in ca. 3:1 ratio, and above 10 °C with IPh(Ctriple bond; length of mdashCR)(OTf) (R = But, SiMe3) to give predominantly o-Tol–Ctriple bond; length of mdashC–Ctriple bond; length of mdashC–R and (o-Tol–Ctriple bond; length of mdashC)2. 31P NMR spectra provide evidence for detection of intermediates. The complexes trans-[Pd(Ctriple bond; length of mdashC-o-Tol)2(PMe2Ph)2] and trans-[PdCl(Ctriple bond; length of mdashC-o-Tol)(PMe2Ph)2] are obtained on reaction of trans-[PdCl2(PMe2Ph)2] with Li(Ctriple bond; length of mdashC-o-Tol) and o-Tol-Ctriple bond; length of mdashCH/Et3N, respectively, and have been characterised by X-ray crystallography.