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KMID : 1059519940380020101
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Journal of the Korean Chemical Society
1994 Volume.38 No. 2 p.101 ~ p.107
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Synthesis and Characterization of Molybdenum(Ⅲ) and (Ⅳ) Complexes with N, P, O-Donating Ligands(Ⅲ)
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Oh Sang-Oh
Lyou Eun-Young
Park Yu-Chul
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Abstract
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Some molybdenum(Ⅲ) and (Ⅳ) complexes have been prepared from the reaction of MoCl4·2MeCN with N, P, O-donating ligands and characterized by elemental analysis, infrared and UV-Visible spectroscopy. 3,5-Lutidine, 1,2-phenylenediamine, 8-hydroxyquinoline, 9,10-phenanthrenequinone, triphenylphosphine and 1,2-bis(diphenylphosphino)ethane were chosen as coordinating ligands. Stretching frequencies υ(Mo-Cl) of Mo(Ⅳ) appear at higher frequencies than those of Mo(Ⅲ) complexes due to the increasing oxidation number of metal. MoCl4(L)2 exhibit one Mo-Cl stretching frequency, whereas MoCl4(L^L) exhibit four Mo-Cl stretching frequencies. The number of Mo-Cl stretching frequency suggestes the former complexes have trans(D4h) and the latter complexes have cis(C2V) symmetry. Stretching frequency ν(C≡N) of acetonitrile in Mo(Ⅲ) complexes are shifted to about 30 cm-1 higher frequency compared with that of a free ligand (2260 cm-1). These spectral data indicates that Mo(Ⅲ) complexes are in the octahedral geometries with the coordinated acetonitrile. Finally each molybdenum(Ⅲ) and (Ⅳ) complexes showed the following formulation; [MoCl4(L)2] [MoCl4(L^L)], [MoCl3(L)2MeCN] and [MoCl3(L^L)MeCN].
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