A new route to sulfur polyimido anions S(NR)(n)(m-): 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). Addit ion of lithium organics to sulfur triimide provides a general route to tria zasulfonates RS(NR)(3)(-). All these anions resemble potential tripodal coo rdination behavior because of their nitrogen donor centers. Furthermore, th e sulfur polyimido ligands are capable of responding to the various require ments of different metals (even in mixed metal species) by charge (de)local ization. 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.