Oxygen Atom Transfer Reactivity of Molybdenum(VI) Complexes Employing Pyrimidine- and Pyridine-2-thiolate Ligands

Four dioxidomolybdenum(VI) complexes of the general structure [MoO₂L₂] employing the S,N-bidentate ligands pyrimidine-2-thiolate (PymS, 1), pyridine-2-thiolate (PyS, 2), 4-methylpyridine-2-thiolate (4-MePyS, 3) and 6-methylpyridine-2-thiolate (6-MePyS, 4) were synthesized and characterized by spectroscopic means and single-crystal X-ray diffraction analysis (2-4). Complexes 1-4 were reacted with PPh₃ and PMe₃, respectively, to investigate their oxygen atom transfer (OAT) reactivity and catalytic applicability. Reduction with PPh₃ leads to symmetric molybdenum(V) dimers of the general structure [Mo₂O₃L₄] (6-9). Kinetic studies showed that the OAT from [MoO₂L₂] to PPh₃ is 5 times faster for the PymS system than for the PyS and 4-MePyS systems. The reaction of complexes 1-3 with PMe₃ gives stable molybdenum(IV) complexes of the structure [MoOL₂(PMe₃)₂] (10-12), while reduction of [MoO₂(6-MePyS)₂] (4) yields [MoO(6-MePyS)₂(PMe₃)] (13) with only one PMe₃ coordinated to the metal center. The activity of complexes 1-4 in catalytic OAT reactions involving Me₂SO and Ph₂SO as oxygen donors and PPh₃ as an oxygen acceptor has been investigated to assess the influence of the varied ligand frameworks on the OAT reaction rates. It was found that [MoO₂(PymS)₂] (1) and [MoO₂(6-MePyS)₂] (4) are similarly efficient catalysts, while complexes 2 and 3 are only moderately active. In the catalytic oxidation of PMe₃ with Me₂SO, complex 4 is the only efficient catalyst. Complexes 1-4 were also found to catalytically reduce NO₃^- with PPh₃, although their reactivity is inhibited by further reduced species such as NO, as exemplified by the formation of the nitrosyl complex [Mo(NO)(PymS)₃] (14), which was identified by single-crystal X-ray diffraction analysis. Computed ΔG^⧧ values for the very first step of the OAT were found to be lower for complexes 1 and 4 than for 2 and 3, explaining the difference in catalytic reactivity between the two pairs and revealing the requirement for an electron-deficient ligand system.