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Inspired by the successful oxidative addition of a P–H bond to univalent Ga[Al(ORF)4] that gives the unprecedented dicationic gallium hydride complex [H–Ga(PPh3)3][Al(ORF)4]2 (ORF = OC(CF3)3), the oxidative addition of E–Cl containing substrates was investigated. The reductive coupling of three PPh2Cl to the catenated phosphorus cation [P3Ph6]+ hinted towards a formal two-electron–three-halide reduction (2e−–3X− reduction). Similarly, from SbCl3, a cationic formal SbI compound and from RhCl3, [RhI(HMB)(COD)]+ and [RhI(COD)2]+ (HMB = C6Me6, COD = 1,5-cyclooctadiene) are formed as [Al(ORF)4]− salts when reacted with Ga+. Thus, Ga[Al(ORF)4] allows for a one-pot 2e−–3X− reduction with the concomitant introduction of a weakly coordinating anion (WCA). [ABSTRACT FROM AUTHOR]

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]