Abstract: | In the presence of N, N′‐dicyclohexylcarbodiimide (DCC), (Bu4N)2Mo6O18(NAr)] ( 1 ) and (Bu4N)2Mo6O17(NAr)2] ( 2 ), Ar = o‐CH3C6H4, have been synthesized via the reaction of α‐Mo8O26]4— with o‐toluidine. If the hydrochloride salt of o‐toluidine was added into the reactive mixture, only the monofunctionalized imido derivative of Mo6O19]2— was obtained; the bifunctionalized derivative of Mo6O19]2— was exclusively synthesized in the presence of non‐protonated o‐toluidine. The molecular and crystal structures of the hybrid compounds 1 and 2 were determined by X‐ray single crystal diffraction, and their UV, IR and NMR spectra were compared. Additionally, a possible reaction mechanism was proposed. |