Organic‐Inorganic Hybrids: Preparation and Structural Characterization of (Bu 4 N) 2 [Mo 6 O 17 (NAr) 2 ] and (Bu 4 N) 2 [Mo 6 O 18 (NAr)] (Ar = o ‐CH 3 C 6 H 4 )

In the presence of N, N′‐dicyclohexylcarbodiimide (DCC), (Bu 4 N) 2 [Mo 6 O 18 (NAr)] ( 1 ) and (Bu 4 N) 2 [Mo 6 O 17 (NAr) 2 ] ( 2 ), Ar = o ‐CH 3 C 6 H 4 , have been synthesized via the reaction of [α‐Mo 8 O 26 ] 4— with o‐ toluidine. If the hydrochloride salt of o‐ toluidine was added into the reactive mixture, only the monofunctionalized imido derivative of [Mo 6 O 19 ] 2— was obtained; the bifunctionalized derivative of [Mo 6 O 19 ] 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.