The complexes of lower valent molybdenum have special nature in the form of coordination and the changeability of valent state. In order to further investigate it, we synthesised the title compounds Ⅰ and Ⅱ which we...The complexes of lower valent molybdenum have special nature in the form of coordination and the changeability of valent state. In order to further investigate it, we synthesised the title compounds Ⅰ and Ⅱ which were trinuclear complexes containing M(O)and determined their crystal structure.展开更多
The reaction of [Et4N][Mo(CO)4(S2CNEt2)] with tetraethylam-monium tetrathiomolybdate affords a new mixed-valence dinuclear molybdenum complex [Et4N]2[(CO)4MoS2MoS2] (1). 1 crystallizes in the orthorhombic space group ...The reaction of [Et4N][Mo(CO)4(S2CNEt2)] with tetraethylam-monium tetrathiomolybdate affords a new mixed-valence dinuclear molybdenum complex [Et4N]2[(CO)4MoS2MoS2] (1). 1 crystallizes in the orthorhombic space group Pbom with a = 18.403(2), b = 11.963(1), c= 13. 482(1)(?) , Z = 4, V = 2986(?)3, Dc=1. 55g/cm3, Mr = 6S2. 69. R =0. 042 and Rw =0. 057 for 1975 independent reflections with I≥3σ(I), F(000) = 1416, μ =11. 2cm-1. The structure of the anion of 1 consists of an octahedron for the lowvalent Mo atom and a tetrahedron for the high-valent Mo atom sharing an S - S edge. The Mo - Mo bond distance is 2. 992 (2) (?) and the bimetallic center MoS2Mo is planar with Mo-S of 2. 517 and 2. 231 A and MoSMo angles of 78. 04° and 77. 67°. The electron delocalization between the two Mo atoms with wide separated oxidation states is also discussed.展开更多
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(1...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.展开更多
文摘The complexes of lower valent molybdenum have special nature in the form of coordination and the changeability of valent state. In order to further investigate it, we synthesised the title compounds Ⅰ and Ⅱ which were trinuclear complexes containing M(O)and determined their crystal structure.
文摘The reaction of [Et4N][Mo(CO)4(S2CNEt2)] with tetraethylam-monium tetrathiomolybdate affords a new mixed-valence dinuclear molybdenum complex [Et4N]2[(CO)4MoS2MoS2] (1). 1 crystallizes in the orthorhombic space group Pbom with a = 18.403(2), b = 11.963(1), c= 13. 482(1)(?) , Z = 4, V = 2986(?)3, Dc=1. 55g/cm3, Mr = 6S2. 69. R =0. 042 and Rw =0. 057 for 1975 independent reflections with I≥3σ(I), F(000) = 1416, μ =11. 2cm-1. The structure of the anion of 1 consists of an octahedron for the lowvalent Mo atom and a tetrahedron for the high-valent Mo atom sharing an S - S edge. The Mo - Mo bond distance is 2. 992 (2) (?) and the bimetallic center MoS2Mo is planar with Mo-S of 2. 517 and 2. 231 A and MoSMo angles of 78. 04° and 77. 67°. The electron delocalization between the two Mo atoms with wide separated oxidation states is also discussed.
基金Project supported by the National Natural Science Foundation of China (No. 29733090-3) and State Key Laboratory of Structural Chemistry.
文摘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.
