Reaction of Molybdenum Hexa-carbonyl with Mercapto-pyridine (PySH) or Mercapto-pyridine Oxide (PyS → O) and Crystal Structure of [Et_4N][Mo_2(PyS)_3(CO)_5]

摘要

Mixed-valence dinuclear molybdenum complex [Et_4N][Mo_2(PyS)_3(CO)_5] (1) (PyS=C_5H_4NS) has been synthesized and characterized by crystallography. 1 crystallizes in monoclinic system with space group P2_1/c with a = 1.5769(11) nm, b = 1.3144(5) run, c = 1.6935(10) nm; β = 111.20(4)°; V = 3.2724 nm~3; Z = 4, D_c = 1.61 g/cm~3, μ = 9.7 cm~(-1) and F(000) = 1600. The final R = 0.054 and wR = 0.073, for 1811 observed reflection with I > 3σ(I). In compound 1, one chelating PyS ligand and two bridging PyS ligands are 3-electron and 5-electron donors, respectively, and two molybdenum atoms are located in different coordination environments resulting in mixed-valence state. The reaction mechanism of Mo(CO)_6 with PySH and PyS → O (C_5H_5SN → O) was investigated and two reaction pathways were proposed.