Role of Organic Fluoride Salts in Stabilizing Niobium Oxo-Clusters Catalyzing Epoxidation.

We present here that easily available organic salts can stabilize/modify niobium (Nb) oxo-clusters. The as-synthesized Nb oxo-clusters have been characterized by various methods. These Nb oxo-clusters were catalytically active for the epoxidation of allylic alcohols and olefins with H2O2 as an oxidant. Notably, Nb-OC@TBAF-0.5 appeared as highly dispersed nanosized particles and showed the highest catalytic activity, which can be attributed to the following reasons on the basis of characterization. First, the strong coordination of fluorine ions with Nb sites and the steric protection with bulky organic cations led to high stabilization and dispersion of the oxo-clusters in the course of the reaction. Second, a hydrogen-bond interaction between the coordinated fluorine atom and the -OH group of allylic alcohol favored the epoxidation reaction. Third, the electron density of Nb sites decreased due to the strong electron-withdrawing ability of F- adjacent to Nb sites, thus promoting the electrophilic oxygen transfer to the C═C bond.

Ionic Liquid Stabilized Niobium Oxoclusters Catalyzing Oxidation of Sulfides with Exceptional Activity.

We present here a new class of niobium oxoclusters that are stabilized effectively by carboxylate ionic liquids. These functionalized ILs are designated as [TBA][LA], [TBA][PA], and [TBA][HPA] in this work, in which TBA represents tetrabutylammonium and LA, PA, and HPA refer to lactate, propionate, 3-hydroxypropionate anions, respectively. The as-synthesized Nb oxoclusters have been characterized by use of elemental analysis, NMR, IR, XRD, TGA, HRTEM. It was found that [TBA][LA]-stabilized Nb oxoclusters (Nb-OC@[TBA][LA]) are uniformly dispersed with an average particle size of 2-3 nm and afforded exceptionally high catalytic activity for the selective oxidation of various thioethers. The turnover number with Nb-OC@[TBA][LA] catalyst was over 56 000 at catalyst loading as low as 0.0033 mol % (1 ppm). Meantime, the catalyst also showed the high activity for the epoxidation of olefins and allylic alcohols by using only 0.065 mol % of catalyst (50 ppm). The characterization of 93 Nb NMR spectra revealed that the Nb oxoclusters underwent structural transformation in the presence of H2 O2 but regenerated to their initial state at the end of the reaction. In particular, the highly dispersed Nb oxoclusters can absorb a large amount of polar organic solvents and thus were swollen greatly, which exhibited "pseudo" liquid phase behavior, and enabled the substrate molecules to be highly accessible to the catalytic center of Nb oxocluster units.

Peroxotantalate-Based Ionic Liquid Catalyzed Epoxidation of Allylic Alcohols with Hydrogen Peroxide.

The efficient and environmentally benign epoxidation of allylic alcohols has been attained by using new kinds of monomeric peroxotantalate anion-functionalized ionic liquids (ILs=[P4,4,4,n ]3 [Ta(O)3 (η-O2 )], P4,4,4,n =quaternary phosphonium cation, n=4, 8, and 14), which have been developed and their structures determined accordingly. This work revealed the parent anions of the ILs underwent structural transformation in the presence of H2 O2 . The formed active species exhibited excellent catalytic activity, with a turnover frequency for [P4,4,4,4 ]3 [Ta(O)3 (η-O2 )] of up to 285 h-1 , and satisfactory recyclability in the epoxidation of various allylic alcohols under very mild conditions by using only one equivalent of hydrogen peroxide as an oxidant. NMR studies showed the reaction was facilitated through a hydrogen-bonding mechanism, in which the peroxo group (O-O) of the peroxotantalate anion served as the hydrogen-bond acceptor and hydroxyl group in the allylic alcohols served as the hydrogen-bond donor. This work demonstrates that simple monomeric peroxotantalates can catalyze epoxidation of allylic alcohols efficiently.