Cationic Niobium‐Sandwich and Piano‐Stool Complexes.

The syntheses of the homoleptic bis(arene) niobium cations [Nb(arene)2]+ (arene = C6H3Me3, C6H5Me) with 16 valence electrons and heteroleptic arene‐carbonyl cations [(CO)Nb(arene)2]+ (arene = C6H3Me3, C6H5Me) and [(arene)M(CO)4]+ (arene = C6H3Me3, C6H6) obeying 18 valence electrons are described. Stabilization of these complexes was achieved by using the weakly coordinating anions [Al(ORF)4]− or [F{Al(ORF)3}2]− (RF = C(CF3)3). The limits of two synthesis routes starting from neutral Nb(arene)2 (arene = C6H3Me3, C6H5Me) or [NEt4][M(CO)6] (M = Nb, Ta) were investigated. All compounds were analyzed by single crystal X‐ray determination, vibrational and NMR spectroscopy. DFT calculations were executed to support the experimental data. [ABSTRACT FROM AUTHOR]