Polyimido sulphur anions S(NR) - mn: Free radicals and coordination behaviour

In a reaction sequence of amide addition followed by halogen oxidation the triazasulphite S(NR) 3^2+ and the tetrazasulphate S(NR) 4^2+ are readily accessible from sulphur diimide S(NR)2 via sulphur triimide S(NR)3. Addition of lithium organics to sulphur triimide provides a general route to triazasulphonates RS(NR) 3^2+ .All these anions resemble potential tripodal coordination behaviour because of their nitrogen donor centres. Furthermore, the sulphur polyimido ligands are capable of responding to the various requirements of different metals (even in mixed metal species) by charge (de)localization. This paper deals with the synthetic routes of the sulphur nitrogen anions and their coordination behaviour. Their reactivity, mainly towards main group metal synthons, is also discussed.