Additions of arenesulphenyl chlorides ( e.g. ArSCI p-XC 6H 4SCl; X Me or Cl; 4-Y-2-O 2NC 6H 4SCl; Y H, Me or NO 2) to R 3MCHCH 2 [R 3MPh 3Si, (EtO) 3Si or Ph 3Ge] can provide both possible adducts: R 3MCHSArCH 2Cl (the anti-Markovnikov adducts) and R 3MCHClCH 2SAr (the Markovnikov adducts). In reactions in CH 2Cl 2 at room temperature, the former adducts always dominate ( > 77%) and can be the exclusive products. The ratio of [R 3MCHSArCH 2Cl]:[R 3MCHClCH 2SAr increases in the sequences Ar p-ClC 6H 4 > o-O 2NC 6H 4 > 2,4-(O 2N) 2C 6H 3; (Me 3SiCHCH 2) > Ph 3SiCHCH2 > (EtO) 3SiCHCH2; and Ph 3SiCHCH 2 > Ph 3GeCHCH 2. A crystal structure determination of (4-Me-2-O 2NC 6H 3S)CH(SiPh 3)CH 2Cl revealed a slightly distorted tetrahedral geometry about Si with a staggered conformation about the central CC bond (SiCCCl dihedral angle is 167°). There is a short S ⋯ O intramolecular distance of 2.781 Å.