Organomercury compounds. IX. Preparations, structures, and thermal decomposition of arylmercuric arenesulphinates

Abstract

The arylmercuric arenesulphinates, PhHg(SO₂Ph), p-MeC₆H₄Hg(SO₂-p-MeC₆H₄), PhHg(SO₂-p-MeC₆H₄), p-MeC₆H₄Hg(SO₂Ph), and C₆F₅Hg(SO₂Ph), have been prepared by reaction of mercuric benzenesulphinate or p- toluenesulphinate with the appropriate diarylmercury compound in chloroform or methanol, and the first three compounds have also been obtained by reaction of liquid sulphur dioxide with diphenylmercury, di-p-tolylmercury, or phenyl-p-tolylmercury. Linkage isomers of phenylmercuric benzenesulphinate have been prepared. Isomer A, obtained from chloroform-pentane, is considered to be a monomeric O-sulphinato complex, and isomer B, obtained from cold acetone, methyl ethyI ketone, or methanol, to be an S-sulphinato complex. The isomers are readily interconverted. In chloroform, deuterochloroform, and acetone, at room temperature, only the O-sulphinato complex can be detected. The other arylmercuric arenesulphinates have the same structure as isomer A. Linkage isomers could not be isolated for these derivatives. However, there is evidence that p-MeC₆H₄Hg(SO₂Ph) slowly isomerizes in the solid state to give the corresponding S-sulphinato complex. Thermal decomposition of PhHg-(SO₂Ph) (both isomers), p-MeC₆H₄Hg(SO₂-p-MeC₆H₄), PhHg(SO₂-p-MeC₆H₄), and p-MeC₈H₄Hg(SO₂Ph) gives sulphur dioxide and the corresponding diarylmercurycompound.