SULFOXIDES AND STEREOCHEMICAL CONTROL IN ORGANOMETALLIC CHEMISTRY

The sulfinyl substituted oxadienes [RS(O)CH=CHC(Me)=O; R = But, Ph] fo rm stable diastereoisomerically pure tricarbonyliron(0) complexes, the relative stereochemistry of which was determined by X-ray crystal str ucture analysis. Phenylsulfinylethene forms a stable tetracarbonyliron (0) complex which is also diastereoisomerically pure. An X-ray crystal structure analysis of this complex revealed its relative stereochemis try and evidence for a through-space interaction between the oxygen at om of the sulfinyl substituent and the carbon atom of one of the metal carbonyl ligands. Dimethyldioxirane efficiently oxidises tricarbonylc hromium(0) complexes of sulfenyl substituted arenes to tricarbonylchro mium(0) complexes of sulfinyl substituted arenes. The diastereoselecti vity of the oxidation of ortho substituted complexes was determined an d found to be dramatically reversed when the sulfenyl substituent is c hanged from methyl to tert-butyl.