Reactions of Hg(OTeF5)(2) with excess amounts of NSF3 at 0 degrees C result in the formation of NSF3 adducts having the compositions [Hg(OTeF5)(2)center dot N equivalent to SF3](infinity) (1), [Hg(OTeF5)(2)center dot 2N equivalent to SF3](2) (2), and Hg-3(OTeF5)(6)center dot 4N equivalent to SF3 (3). When the reactions are carried out at room temperature, oxygen/fluorine metatheses occur yielding the F2OSN- derivatives [Hg(OTeF5)(N=SOF2)center dot N equivalent to SF3](infinity) (4) and [Hg-3(OTeF5)(5)(N=SOF2)center dot 2N equivalent to SF3](2) (5). The proposed reaction pathway leading to F2OSN- group formation occurs by nudeophilic attack by a F5TeO- group at the sulfur(VI) atom of NSF3, followed by TeF6 elimination. Tellurium hexafluoride formation was confirmed by F-19 NMR spectroscopy. The NSF3 molecules are terminally N-coordinated to mercury, whereas the F2OSN- ligands are N-bridged to two mercury atoms. The compound series was characterized by low-temperature single-crystal X-ray diffraction and low-temperature Raman spectroscopy. Several structural motifs are observed within this structurally diverse series. These include the infinite chain structures of the related compounds, 1 and 4; 2, a dimeric structure which possesses an (HgO mu)(2) ring at its core; 3, a structure based on a cage comprised of a (HgO mu)(3) ring that is capped on each face by mu(3)-oxygen bridged F5TeO- groups; and 5, a dimeric structure possessing two distorted (Hg3O2N) rings that are formally derived from 3 by replacement of a F5TeO- group by a F2OSN- group in each ring. Quantum-chemical calculations were carried out to gain insight into the bonding of the mu(3)-oxygen bridged teflate groups observed in structure 3. Compounds 1-5 represent a novel class of neutral transition metal complexes with NSF3, providing the first examples of NSF3 coordination to mercury. Compounds 4 and 5 also provide the only examples of F2OSN- derivatives of mercury that have been characterized by single-crystal X-ray diffraction.