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

Sharma, Manab; Canty, Allan J.; Gardiner, Michael G.; Jones, Roderick C.

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

Date

2011-04-01

Authors

Abstract

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