The d0, d1, and d2 Configurations in Known and Unknown Tetrathiometal Compounds MS4n- (M = Mo, Tc, Ru; W, Re, Os). A Quantum Chemical Study
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Inorganic Chemistry 38 (26): 6101--6105 (1999)

The known tetrathiometalates MoS42-/3-, WS42-/3-, ReS4-/2-/3-, and the unknown species TcS4-/2-, RuS40/-, and OsS40/-/2- were calcd. using ab initio and DFT methods. The one-electron reduced species with d1 configuration were shown to exhibit a slight Jahn-Teller distortion (Td $\rightarrow$ D2d); the largest corresponding stabilization energy was obtained for MoS43- with -4.17 kcal/mol. Trends in vacuum bonding energies involve a destabilization on going from 5dn to 4dn systems and on redn. from d0 to d1 species, with the exception of Ru and Os complexes where the d1 configurations are more stable than the d0 forms. The d2 species ReS43- and OsS42- have vacuum bonding energies similar to those of d1 analogs. The metal contribution to the LUMO (e) of d0 forms is lowest for the neutral RuS4 and OsS4 and highest for the dianions MoS42- and WS42-. The DFT approach supported by correlated ab initio calcns. describes the main features of the electronic spectra of the d0 complexes. For the exptl. best accessible ReS4n- system the absorption energies and stretching frequencies were well reproduced, and the related but hitherto unknown OsS4- ion is predicted to be a fairly stable paramagnetic species. on SciFinder(R)
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