The reactivity of MoCl5 with molecules containing the alcohol functionality

The 1:1 M reaction of MoCl5 with Cl(CH2)2OH, in dichloromethane at room temperature, proceeded with chlorine–oxygen interchange and HCl release to give MoOCl3 in 65% yield. The analogous reactions involving iPrOH, MeOH, L-menthol and H2O gave impure MoOCl3. MoCl5 reacted with Me2N(CH2)2OH in 1:1 M ratio affording the 2-chloroammonium salt [Me2NH(CH2)2Cl]2[Mo2O2Cl8], 1. The reaction of MoCl5 with MeO(CH2)2OH afforded a mixture of [Mo(O(CH2)2OMe)2Cl2][Mo2O2Cl7], 2a, and [Mo(O(CH2)2OMe)2Cl2][MoOCl4], 2b. The products 1, 2a and 2b were characterized by analytical and spectroscopic techniques, and by X-ray diffractometry. The X-ray structure of 2b shows weak anion–anion interactions, therefore 2b might be alternatively viewed as a [Mo2O2Cl8]2- salt.