Alkyl-vinyl-ethers from alcoholic substrates and the Zeise’s salt, via square planar [PtCl(N–N)(η1-CH2CH2OR)] complexes

Complexes of the type [PtCl(N–N)(η1-CH2CH2OR)], N–N = diimine ligand, R = alkyl, were generally considered to be indefinitely stable, both in solution and in the solid state. Unexpectedly we found that complexes of the type [PtCl(Me2phen)(η1-CH2CH2OR)], Me2phen = 2,9-dimethyl-1,10-phenatroline, R = alkyl, undergo spontaneous decomposition, to give the corresponding vinyl-ether, CH2double bond; length as m-dashCHOR. Decomposition pathway studies suggest a pseudo-Wacker type mechanism (β H− shift process) activated by sterical hindrance in the Pt(II) coordination plane, due to the Me2phen ligand sterically induced distortions in the Pt(II) coordination plane. A new useful synthetic pathway to access valuable and low toxic alkyl-vinyl-ethers is here reported.