Aromatic mercuration. The reaction of mercury(II) acetate with p-tolyltrimethylsilane and with anisole

Abstract

Both mercuridesilylation of p-tolyltrimethylsilane and mercuration of anisole by mercury(II) acetate in glacial acetic acid involve both un-ionized mercury(II) acetate and positive acetatomercury(II) ions as electrophiles. The positive ion is at least 15 times more reactive than molecular mercury(II) acetate in the mercuridesilylation, and at least twice as reactive in the mercuration. Activation parameters for mercuration and mercuridesilylation are similar, and indicate a highly ordered activated complex. The rate of mercuridesilylation increases with increase in the water content of the solvent, and is also affected by the silane concentration and by other non-polar molecules, whereas the mercuration of anisole is unaffected by such factors. The equilibrium constant for the formation of the triacetatomercurate(II) anion has been obtained from the kinetic data and independently measured.