Two new bromo-functionalized organoimido derivatives of hexamolybdate: Synthesis, crystal structure, spectroscopic and electrochemical studies

Two organic–inorganic hybrid compounds, (Bu4N)2[Mo6O18(NAr)] (Ar =  2-CH3-4-BrC6H3 (1) or 2,6-CH3-4-BrC6H2 (2)) have been synthesized via the DCC dehydrating protocol of the reaction of [α-Mo8O26]4− with 2-methyl-4-bromoaniline hydrochloride or 2,6-dimethyl-4-bromoaniline hydrochloride in anhydrous acetonitrile, which have been characterized by UV–Vis spectra, 1H NMR, IR, cyclic voltammetry and X-ray single-crystal diffraction study. Both compounds crystallize in the monoclinic space group P1¯, which are featured in a terminal phenylimido group linked to a Mo atom of a hexamolybdate cluster by a Mo–N triple bond. Interestingly, there are two conformational isomers of the cluster anions of 1 and 2 in the crystals. By cyclic voltammetry study, their special redox properties were also found in the end.

Such two cluster anions now can be prepared in high purity and excessive yields by the reaction of [α-Mo8O26]4− and hydrochloride salts of corresponding aromatic amine bromides with DCC as a dehydrating agent in dry and hot acetonitrile solution.Figure optionsDownload as PowerPoint slideFigure optionsDownload as PowerPoint slide