Cationic complexes of the ‘3+1’ oxorhenium–thiolate family

The ‘3+1’ concept of ligand addition to Group VII metaloxo species allows the facile preparation of neutral complexes of the general type [MO(SXY)(SR)], where X=S, O, or N and Y=S or O. However, if appropriate amine functionalities are incorporated into the substituent R of the monodentate ligand, cationic oxometalate complexes of the type [MO(SXY)(SRNHx)]+ may be routinely prepared. The synthesis and characterization of a series of complexes of this general class are reported. The structures of [ReO{(SCH2CH2)2S}(C5H4NH-2-S)][Br], [ReO{(SCH2CH2)2S}(C5H4NH-4-S)][Br], [ReO{(SCH2CH2)2S}(SCH2CH2NH3)][Cl], and [ReO{C5H3N-2-CH2O-6-CH2S}(C5H4NH-2-S)}][Br] are described and compared to other examples of ‘3+1’ oxorhenium thiolate complexes.