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

AbstractMixed‐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.