On the Structural Dichotomy of Cationic, Anionic, and Neutral FeS(2).

Structural and thermochemical aspects of the FeS(2)(+) cation are examined by different mass spectrometric methods and ab initio calculations using density functional theory. Accurate threshold measurements provide thermochemical data for FeS(+), FeS(2)(+), and FeCS(+), i.e., D(0)(Fe(+)-S) = 3.06 +/- 0.06 eV, D(0)(SFe(+)-S) = 3.59 +/- 0.12 eV, D(0)(Fe(+)-S(2)) = 2.31 +/- 0.12 eV, and D(0)(Fe(+)-CS) = 2.40 +/- 0.12 eV. Fortunate circumstances allow a refinement of the data for FeS(+) by means of ion/molecule equilibria, and the resulting D(0)(Fe(+)-S) = 3.08 +/- 0.04 eV is among the most precisely known binding energies of transition-metal compounds. The present results agree with previous experimental findings and also corroborate the computed data for FeS(+) and FeS(2)(+). Ab initio calculations predict a sextet ground state ((6)A(1)) for FeS(2)(+) with a cyclic structure. The presence of S-S and Fe-S bonds accounts for the fact that not only reactions involving the disulfur unit but also sulfur-atom transfer can occur. In contrast, the FeS(2)(-) anion is an acyclic iron disulfide. In the gas phase, neutral FeS(2) may adopt either acyclic or cyclic structures, which are rather close in energy according to the calculations.