A new route to sulfur polyimido anions S(NR)nm-:: reactivity and coordination behavior

In a reaction sequence of amide addition followed by halogen oxidation the triazasulfite S(NR)(3)(2-) and the tetrazasulfate S(NR)(4)(2-) are readily accessible from sulfur diimide S(NR)(2) via sulfur triimide S(NR)(3). Addition of lithium organics to sulfur triimide provides a general route to triazasulfonates RS(NR)(3)(-). All these anions resemble potential tripodal coordination behavior because of their nitrogen donor centers. Furthermore, the sulfur polyimido ligands are capable of responding to the various requirements of different metals (even in mixed metal species) by charge (de)localization. This review deals with the synthetic routes to the sulfur nitrogen anions and with their coordination behavior. The reactivity mainly towards main group metal synthons is discussed. (C) 1998 Elsevier Science S.A. All rights reserved.