Addition of sulphenyl halides to alkenyl-metal compounds III. Arenesulphenyl chloride additions to triethoxy- and triphenylvinylsilanes and to triphenylvinylgermanium. Crystal structure of (4-Me-2-O2NC6H3S)CH(SiPh3)CH2Cl

Article abstract of DOI:10.1016/0022-328X(92)83436-L

Additions of arenesulphenyl chlorides (e.g.ArSCl=p-XC6H4SCl; X=Me or Cl; 4-Y-2-O2NC6H4SCl; Y=H, Me or NO2) to R3MCH=CH2 can provide both possible adducts: R3MCHSArCH2Cl (the anti-Markovnikov adducts) and R3MCHClCH2SAr (the Markovnikov adducts).In reactions in CH2Cl2 at room temperature, the former adducts always dominate (>77percent) and can be the exclusive products.The ratio of : increases in the sequences Ar=p-ClC6H4 > o-O2NC6H4 > 2,4-(O2N)2C6H3; (Me3SiCH=CH2) > Ph3SiCH=CH2 > (EtO)3SiCH=CH2; and Ph3SiCH=CH2 > Ph3GeCH=CH2.A crystal structure determination of (4-Me-2-O2NC6H3S)CH(SiPh3)CH2Cl revealed a slightly distorted tetrahedral geometry about Si with a staggered conformation about the central C-C bond (Si-C-C-Cl dihedral angle is 167 deg).There is a short S...O intramolecular distance of 2.781 Angstroem.