The reactivity of Molybdenum Pentachloride with Ester Molecules: Ester Activation, Metal Reduction, and Synyhesis of 1D Coordination Polymers

The reactions of Mo2Cl10 (1) with stoichiometric amounts of a variety of molecules containing the ester functionality in anhydrous noncoordinating solvents afforded metal compounds, which were isolated in the solid state and characterized. The 1: 4 molar reactions of 1 with methyl formate (HCO2Me), methyl methoxyacetate (MeOCH2CO2Me) and methyl D,L-lactate [D,L-HOCH(Me)CO2Me] gave the dinuclear complex [MoOCl3{O=C(H)OMe}](2) (2) and the mononuclear complexes MoOCl3[kappa(2)-O=C(OMe)CH2OMe] (6a) and MoOCl3[kappa(2)-O=C(OMe)CH(Me)OH] (6b), respectively. According to NMR/GC-MS analyses, activation of the ester moiety in part of the organic material took place in distinct cases. The molybdenum(IV) 1D coordination polymers [MoCl4-kappa(2)-{trans-(CO2R)CH=CH(CO2R)}](n) (R = Me, 3a; R = Et, 3b) were prepared by treatment of 1 with 2 equiv. of alkyl fumarates. In contrast, the mononuclear Mo-IV complexes MoCl4[kappa(2)-CH2(CO2Me)(2)] (4) and MoCl4[kappa(2)-{cis-(CO2Me)CH=CH(CO2Me)}] (5) were obtained from 1/CH2(CO2Me)(2) and 1/cis-maleate, respectively. The molecular structures of 2, 3a, 3b, 4, 6a and 6b were ascertained by X-ray diffraction studies.