Neutral thiolates of antimony(III) and bismuth(III)

A range of bismuth(III) and antimony(III) thiolates, Bi(SR)3(R = C6F5, 4-MeC6H4, 2,6-Me2C6H3 or 3,5-Me2C6H3) and Sb(SR)3(R = 4-MeC6H4 or 3,5-Me2C6H3) has been synthesised and the structures of the two antimony complexes have been determined. Both structures reveal a trigonal-pyramidal antimony centre bonded to three thiolate groups with, for the 4-MeC6H4 complex, additional intermolecular Sb ⋯ S interactions and, for the 3,5-Me2C6H3 complex, intermolecular arene to antimony interactions. The syntheses and structures of the organotransition-metal complexes [Bi(SC6F5){M(CO)3(η-C5H5)}2](M = Mo or W) are also reported in which the bismuth centre is bonded to one SC6F5 group and two M(CO)3(η-C5H5) fragments with no short intermolecular interactions.