Coordination chemistry of sulfines I. Synthesis and characterization of the complexes Pt(PPh3)2(XYCSO) (X,Y = aryl, S-aryl, S-alkyl, Cl). Coordination via the C=S-p- bond

Abstract

Reactions of Pt(PPh{3}){4} with the sulfines, XYC@?S@?O, (X, Y = aryl, S-aryl, S-alkyl, Cl) yield coordination compounds of the type Pt(PPh{3}){2}(XYCSO). Infrared, }3{}1{P and }1{H NMR spectra reveal that in all cases the sulfine ligand is coordinated side-on via the C@?S @p-bond (Pt-@h}2{-CS). Reactions of Pt(PPh{3}){4} with either the E- or Z-isomer of (p-CH{3}C{6}H{4})(CH{3}S)CSO yields the corresponding E- or Z-coordination compound, Pt(PPh{3}){2}[E-(p-CH{3}C{6}H{4})(CH{3}S)CSO] or Pt(PPh{3}){2}[Z-(p-CH{3}C{6}H{4})(CH{3}S)CSO], indicating that the configuration of the sulfine ligand is retained upon coordination to the Pt(PPh{3}){2} unit. The compounds Pt(PPh{3}){2}(XYCSO), containing reactive C@?X and/or C@?Y bonds (X, Y = S-aryl, S-alkyl, Cl), undergo a rearrangement in solution to give complexes of the type PtX(PPh{3}){2}(YCSO).