Antimony( 111) and bismuth (111) complexes of sterically demanding arenechalcogenolato ligands, M(EC,H,R',-2.4,6), (E = S or Se; M = Sb or Bi; R' = Me, Pri or But) have been prepared by either protolysis of the amides M [N(SiMe,),], with arenechalcogenols, or from MCI, by halide exchange (M = Bi or Sb). The complexes are monomeric in the solid state and sublime readily. The crystal structure of Sb( SC,H2Prl,-2,4,6), has been determined by X-ray diffraction. The compound possesses a trigonal-pyramidal geometry, with Sb-S distances of 2.41 8(2)-2.438(2) A and S-Sb-S angles of 94.69(7)-98.29(8)". Preliminary X-ray results on Bi(SeC6H2Pra,-2,4,6), showed that the compounds of Sb and Bi are isostructural. Thermolytic decomposition of some of the compounds has been carried out in the solid state. Compounds with R' = Me or Pri undergo reductive elimination to give elemental bismuth or antimony, whereas the bulky selenolates M (SeC6H,But,-2,4,6), afford M,Se,.