Molybdenum(VI) oxosulfato complexes in MoO3-K2S2O7-K2SO4 molten mixtures: stoichiometry, vibrational properties, and...

The structural and vibrational properties of molybdenum(VI) oxosulfato complexes formed in MoO(3)–K(2)S(2)O(7) and MoO(3)–K(2)S(2)O(7)–K(2)SO(4) molten mixtures under an O(2) atmosphere and static equilibrium conditions were studied by Raman spectroscopy at temperatures of 400–640 °C. The corresponding composition effects were explored in the X(MoO)(3)(0) = 0–0.5 range. MoO(3) undergoes a dissolution reaction in molten K(2)S(2)O(7), and the Raman spectra point to the formation of molybdenum(VI) oxosulfato complexes. The Mo═O stretching region of the Raman spectrum provides sound evidence for the occurrence of a dioxo Mo(═O)(2) configuration as a core. The stoichiometry of the dissolution reaction MoO(3) + nS(2)O(7)(2–) → C(2n–) was inferred by exploiting the Raman band intensities, and it was found that n = 1. Therefore, depending on the MoO(3 content, monomeric MoO(2)(SO(4))(2)(2–) and/or associated [MoO(2)(SO(4))(2)](m)(2m–) complexes are formed in the binary MoO(3)–K(2)S(2)O(7) molten system, and pertinent structural models are proposed in full consistency with the Raman data. A 6-fold coordination around Mo is inferred. Adjacent MoO(2)(2+) cores are linked by bidentate bridging sulfates. With increasing temperature at concentrated melts (i.e., high X(MoO)(3)(0)), the observed spectral changes can be explained by partial dissociation of [MoO(2)(SO(4))(2)](m)(2m–) by detachment of S(2)O(7)(2–) and formation of a Mo—O—Mo bridge. Addition of K(2)SO(4) in MoO(3)–K(2)S(2)O(7) results in a “follow-up” reaction and formation of MoO(2)(SO(4))(3)(4–) and/or associated [MoO(2)(SO(4))(3)](m)(4m–) complexes in the ternary MoO(3)–K(2)S(2)O(7)–K(2)SO(4) molten system. The 6-fold Mo coordination comprises two oxide ligands and four O atoms linking to coordinated sulfate groups in various environments of reduced symmetry. The most characteristic Raman bands for the molybdenum(VI) oxosulfato complexes pertain to the Mo(═O)(2) stretching modes: (1) at 957 (polarized) and 918 (depolarized) cm(–1) for the ν(s) and ν(as) Mo(═O)(2) modes of MoO(2)(SO(4))(2)(2–) and [MoO(2)(SO(4))(2)](m)(2m–) and (2) at 935 (polarized) and 895 (depolarized) cm(–1) for the respective modes of MoO(2)(SO(4))(3)(4–) and [MoO(2)(SO(4))(3)](m)(4m–). The results were tested and found to be in accordance with ab initio quantum chemical calculations carried out on [MoO(2)(SO(4))(3)](4–) and [{MoO(2)}(2)(SO(4))(4)(μ-SO(4))(2)](8–) ions, in assumed isolated gaseous free states, at the DFT/B3LYP (HF) level and with the 3-21G basis set. The calculations included determination of vibrational infrared and Raman spectra, by use of force constants in the Gaussian 03W program.