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]  

作　　者：庄伯涛 余佩华 黄梁仁 何玲洁 周张锋 吴克琛 

机构地区：[1]Institute of Research on the Structure of Matter, State Key Laboratory of Structural Chemistry, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China

出　　处：《Chinese Journal of Chemistry》2004年第11期1291-1296,共6页中国化学（英文版）

基　　金：Project supported by the National Natural Science Foundation of China (No. 29733090-3) and State Key Laboratory of Structural Chemistry.

摘　　要：Mixed-valence dinuclear molybdenum complex [Et4N][Mo2(PyS)3(CO)5] (1) (PyS=C5H4NS) has been synthe-sized 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; b=111.20(4); V=3.2724 nm3; Z=4, Dc=1.61 g/cm3, =9.7 cm-1 and F(000)=1600. The final R=0.054 and wR=0.073, for 1811 observed reflection with I>3s(I). In compound 1, one chelating PyS ligand and two bridging PyS ligands are 3-electron and 5-electron donors, respec-tively, 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 PySO (C5H5SNO) was investigated and two reac-tion pathways were proposed.Mixed-valence dinuclear molybdenum complex [Et4N][Mo2(PyS)3(CO)5] (1) (PyS=C5H4NS) has been synthe-sized 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; b=111.20(4); V=3.2724 nm3; Z=4, Dc=1.61 g/cm3, =9.7 cm-1 and F(000)=1600. The final R=0.054 and wR=0.073, for 1811 observed reflection with I>3s(I). In compound 1, one chelating PyS ligand and two bridging PyS ligands are 3-electron and 5-electron donors, respec-tively, 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 PySO (C5H5SNO) was investigated and two reac-tion pathways were proposed.

关 键 词：mixed-valence Mo-PyS complexe synthesis crystal structure PySO 

分 类 号：O614[理学—无机化学]