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

The reactions of Mo 2 Cl 10 ( 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 (HCO 2 Me), methyl methoxyacetate (MeOCH 2 CO 2 Me) and methyl D , L ‐lactate [ D , L ‐HOCH(Me)CO 2 Me] gave the dinuclear complex [MoOCl 3 {O=C(H)OMe}] 2 ( 2 ) and the mononuclear complexes MoOCl 3 [κ 2 ‐O=C(OMe)CH 2 OMe] ( 6a ) and MoOCl 3 [κ 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 [MoCl 4 ‐κ 2 ‐{ trans ‐(CO 2 R)CH=CH(CO 2 R)}] 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 MoCl 4 [κ 2 ‐CH 2 (CO 2 Me) 2 ] ( 4 ) and MoCl 4 [κ 2 ‐{ cis ‐(CO 2 Me)CH=CH(CO 2 Me)}] ( 5 ) were obtained from 1 /CH 2 (CO 2 Me) 2 and 1 / cis ‐maleate, respectively. The molecular structures of 2 , 3a , 3b , 4 , 6a and 6b were ascertained by X‐ray diffraction studies.