Reaction of molybdenum hexa-carbonyl with mercapto-pyridine (PySH) or mercapto-pyridine oxide (PyS→O) and crystal structure of [Et4N][Mo2(PyS)3(CO)5]
Abstract
Mixed-valence dinuclear molybdenum complex [Et4N][ Mo2(PyS)3(CO)5] (1) (PyS=C5H4NS) has been synthesized and characterized by crystallography. 1 crystallizes in monoclinic system with space group P21/c with a= 1.5769(11) nm, b= 1.3144(5) nm, c= 1.6935(10) nm; β= 111.20(4)o; V=3.2724 nm3; Z=4, Dc=l.61 g/cm3, μ= 9.7 cm−' and F(000)=1600. The final R=0.054 and wR=0.073, for 1811 observed reflection with I >3@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 (C5H5SN→O) was investigated and two reaction pathways were proposed.
