Ferrocenium Ions as Catalysts: Decomposition Studies and Counteranion Influence on Catalytic Activity

Catalyst decomposition has a negative effect on catalytic activity, and knowledge of decomposition pathways can assist with catalyst development. Ferrocenium cations have been employed as catalysts in a number of organic transformations, and we investigated the stability of a number of ferrocenium salts in solution. The observed rate decomposition constants for [Fc]Cl, [Fc]PF6, [Fc]BF4, [Fc]CSA [Fc = ferrocenium, CSA = camphor-10-sulfonate (β)], [AcFc]SbF6, (AcFc = acetylated ferrocene), and [FcB(OH)2]SbF6 [FcB(OH)2 = ferrocenylboronic acid] were determined in CH2Cl2 solution by time-resolved UV-vis spectroscopy. The rate decomposition constants depended on the nature of the counterion, with [Fc]Cl being the most stable complex in solution. The decomposition rate constants dropped by roughly an order of magnitude in most cases when the experiments were performed in nitrogenated solvent, demonstrating that the decomposition is mainly an oxidative process. The cosolvent HFIP (1,1,1,3,3,3-hexafluoropropan-2-ol) slowed the decomposition of the ferrocenium cations as well. Many catalytic or stoichiometric reactions of ferrocenium cations are performed with alcohols; we determined that hexan-1-ol is decomposed over the course of 16 hours, but not oxidized in the presence of a ferrocenium cation. Finally, the different ferrocenium cations were employed in a test reaction to determine catalytic activity. The nucleophilic substitution of hydroxyl groups in a tertiary propargylic alcohol by an alcohol is catalyzed by all complexes, and, again, a counterion dependency of the catalytic activity was observed. Also, HFIP increases the catalytic activity of the ferrocenium cations. The research has importance in the development of ferrocenium-based catalyst systems, because changes in the counterion as well as the architecture of the ferrocenium cation have an influence on stability and catalytic activity.

Solid State Structure of Bis[(bromo)(dicyclopentadienyl)vanadium(μ2-fluoro)][(bromo)(cyclopentadienyl)vanadium][tetrafluoroborate]

The new complex [V(C5H5)2Br]2(μ2-F)2[V(C5H5)Br]+[BF4]− has been isolated from the reaction of vanadocene monobromide with the ferrocenium cation. The complex is a mixed valence compound composed of two V(IV) and one V(III) centers. The V(III) center has one cyclopentadienyl ligand in its coordination sphere, as well as a bromide and two fluoride ligands. Each fluoride ligand is also attached to one of the V(IV) centers, which additionally is coordinated by a bromide and two cyclopentadienyl ligands. The complex crystallizes in the monoclinic space group P21/m, with a=7.66490(10) Å, b=15.2457(2) Å, c=13.3185(2) Å, and β=101.2721(8)° at 150(1) K.