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(CΞC-o-Tol)2(PMe2Ph)2] and trans-[PdCl(CΞC-o-Tol)(PMe2Ph)2]

Trans-di(ortho-tolylethynyl)bis(dimethylphenylphosphine)palladium(II) reacts above -20 degrees C with the iodoniumreagent IPhCl(2) to give predominantly o-Tol-C equivalent to C-Cl, above 15 degrees C with IPh(2)(OTf) (OTf=triflate) to give o-Tol-C C-Ph and (o-Tol-C C)(2) in ca. 3:1 ratio, and above 10 degrees C with IPh(C R)(OTf) (R = Bu(t), SiMe(3)) to give predominantly o-Tol-C C-C C-R and (o-Tol-C C)(2). (31)P NMR spectra provide evidence for detection of intermediates. The complexes trans-[Pd(C C-o-Tol)(2)(PMe(2)Ph)(2)] and trans-[PdCl (C C-o-Tol)(PMe(2)Ph)(2)] are obtained on reaction of trans-[PdCl(2)(PMe(2)Ph)(2)] with Li(C C-o-Tol) and o-Tol-C CH/Et(3)N, respectively, and have been characterised by X-ray crystallography.