Tuning Reactivity of Zr-Substituted Keggin Phosphotungstate in Alkene Epoxidation through Balancing H2O2 Activation Pathways: Unusual Effect of Base.

The Zr-monosubstituted Keggin-type dimeric phosphotungstate (Bu4N)8[{PW11O39Zr(µ-OH)(H2O)}2] (1) efficiently catalyzes epoxidation of C═C bonds in various kinds of alkenes, including terminal ones, with aqueous H2O2 as oxidant. Less sterically hindered double bonds are preferably epoxidized despite their lower nucleophilicity. Basic additives (Bu4NOH) in the amount of 1 equiv per dimer 1 suppress H2O2 unproductive decomposition, increase substrate conversion, improve yield of heterolytic oxidation products and oxidant utilization efficiency, and also affect regioselectivity of epoxidation, enhancing oxygen transfer to sterically hindered electron-rich C═C bonds. Acid additives produce a reverse effect on the substrate conversion and H2O2 efficiency. The reaction mechanism was explored using a range of test substrates, kinetic, and spectroscopic tools. The opposite effects of acid and base additives on alkene epoxidation and H2O2 degradation have been rationalized in terms of their impact on hydrolysis of 1 to form monomeric species, [PW11O39Zr(OH)(H2O)x]4- (1-M, x = 1 or 2), which favors H2O2 homolytic decomposition. The interaction of 1 with H2O2 has been investigated by HR-ESI-MS, ATR-FT-IR, and 31P NMR spectroscopic techniques. The combination of spectroscopic studies and kinetic modeling implicated the existence of two types of dimeric peroxo complexes, [Zr2(µ-η2:η2-O2){PW11O39}2(H2O)x]]8- and [{Zr(µ-η2-O2)}2(PW11O39)2(H2O)y]10-, along with monomeric Zr (hydro)peroxo species that begin to dominate at a high excess of H2O2. Both dimeric µ-η2-peroxo intermediates are inert toward alkenes under stoichiometric conditions. V-shape Hammett plots obtained for epoxidation of p-substituted styrenes suggested a biphilic nature of the active oxidizing species, which are monomeric Zr-hydroperoxo and peroxo species. Small basic additives increase the electrophilicity of the catalyst and decrease its nucleophilicity. HR-ESI-MS has identified a dimeric, most likely, bridging hydroperoxo species [{PW11O39Zr}2(µ-O)(µ-OOH)]9-, which may account for the improved epoxidation selectivity and regioselectivity toward sterically hindered C═C bonds.

Resolving the Mechanism for H2O2 Decomposition over Zr(IV)-Substituted Lindqvist Tungstate: Evidence of Singlet Oxygen Intermediacy.

The decomposition of hydrogen peroxide (H2O2) is the main undesired side reaction in catalytic oxidation processes of industrial interest that make use of H2O2 as a terminal oxidant, such as the epoxidation of alkenes. However, the mechanism responsible for this reaction is still poorly understood, thus hindering the development of design rules to maximize the efficiency of catalytic oxidations in terms of product selectivity and oxidant utilization efficiency. Here, we thoroughly investigated the H2O2 decomposition mechanism using a Zr-monosubstituted dimeric Lindqvist tungstate, (Bu4N)6[{W5O18Zr(µ-OH)}2] ({ZrW5}2), which revealed high activity for this reaction in acetonitrile. The mechanism of the {ZrW5}2-catalyzed H2O2 degradation in the absence of an organic substrate was investigated using kinetic, spectroscopic, and computational tools. The reaction is first order in the Zr catalyst and shows saturation behavior with increasing H2O2 concentration. The apparent activation energy is 11.5 kcal·mol-1, which is significantly lower than the values previously found for Ti- and Nb-substituted Lindqvist tungstates (14.6 and 16.7 kcal·mol-1, respectively). EPR spectroscopic studies indicated the formation of superoxide radicals, while EPR with a specific singlet oxygen trap, 2,2,6,6-tetramethylpiperidone (4-oxo-TEMP), revealed the generation of 1O2. The interaction of test substrates, α-terpinene and tetramethylethylene, with H2O2 in the presence of {ZrW5}2 corroborated the formation of products typical of the oxidation processes that engage 1O2 (endoperoxide ascaridole and 2,3-dimethyl-3-butene-2-hydroperoxide, respectively). While radical scavengers tBuOH and p-benzoquinone produced no effect on the peroxide product yield, the addition of 4-oxo-TEMP significantly reduced it. After optimization of the reaction conditions, a 90% yield of ascaridole was attained. DFT calculations provided an atomistic description of the H2O2 decomposition mechanism by Zr-substituted Lindqvist tungstate catalysts. Calculations showed that the reaction proceeds through a Zr-trioxidane [Zr-η2-OO(OH)] key intermediate, whose formation is the rate-determining step. The Zr-substituted POM activates heterolytically a first H2O2 molecule to generate a Zr-peroxo species, which attacks nucleophilically to a second H2O2, causing its heterolytic O-O cleavage to yield the Zr-trioxidane complex. In agreement with spectroscopic and kinetic studies, the lowest-energy pathway involves dimeric Zr species and an inner-sphere mechanism. Still, we also found monomeric inner- and outer-sphere pathways that are close in energy and could coexist with the dimeric one. The highly reactive Zr-trioxidane intermediate can evolve heterolytically to release singlet oxygen and also decompose homolytically, producing superoxide as the predominant radical species. For H2O2 decomposition by Ti- and Nb-substituted POMs, we also propose the formation of the TM-trioxidane key intermediate, finding good agreement with the observed trends in apparent activation energies.

UiO-66 framework with an encapsulated spin probe: synthesis and exceptional sensitivity to mechanical pressure.

Probes sensitive to mechanical stress are in demand for the analysis of pressure distribution in materials, and the design of pressure sensors based on metal-organic frameworks (MOFs) is highly promising due to their structural tunability. We report a new pressure-sensing material, which is based on the UiO-66 framework with trace amounts of a spin probe (0.03 wt%) encapsulated in cavities. To obtain this material, we developed an approach for encapsulation of stable nitroxide radical TEMPO ((2,2,6,6-tetramethylpiperidin-1-yl)oxyl) into the micropores of UiO-66 during its solvothermal synthesis. Pressure read-out using electron paramagnetic resonance (EPR) spectroscopy allows monitoring the degradation of the defected MOF structure upon pressurization, where full collapse of pores occurs at as low a pressure as 0.13 GPa. The developed methodology can be used in and ex situ and provides sensitive tools for non-destructive mapping of pressure effects in various materials.

Catalytic Performance of Zr-Based Metal-Organic Frameworks Zr-abtc and MIP-200 in Selective Oxidations with H2 O2.

The catalytic performance of Zr-abtc and MIP-200 metal-organic frameworks consisting of 8-connected Zr6 clusters and tetratopic linkers was investigated in H2 O2 -based selective oxidations and compared with that of 12-coordinated UiO-66 and UiO-67. Zr-abtc demonstrated advantages in both substrate conversion and product selectivity for epoxidation of electron-deficient C=C bonds in α,ß-unsaturated ketones. The significant predominance of 1,2-epoxide in carvone epoxidation, coupled with high sulfone selectivity in thioether oxidation, points to a nucleophilic oxidation mechanism over Zr-abtc. The superior catalytic performance in the epoxidation of unsaturated ketones correlates with a larger amount of weak basic sites in Zr-abtc. Electrophilic activation of H2 O2 can also be realized, as evidenced by the high activity of Zr-abtc in epoxidation of the electron-rich C=C bond in caryophyllene. XRD and FTIR studies confirmed the retention of the Zr-abtc structure after the catalysis. The low activity of MIP-200 in H2 O2 -based oxidations is most likely related to its specific hydrophilicity, which disfavors adsorption of organic substrates and H2 O2 .

Nucleophilic versus Electrophilic Activation of Hydrogen Peroxide over Zr-Based Metal-Organic Frameworks.

Zr-based metal-organic frameworks (Zr-MOF) UiO-66 and UiO-67 catalyze thioether oxidation in nonprotic solvents with unprecedentedly high selectivity toward corresponding sulfones (96-99% at ca. 50% sulfide conversion with only 1 equiv of H2O2). The reaction mechanism has been investigated using test substrates, kinetic, adsorption, isotopic (18O) labeling, and spectroscopic tools. The following facts point out a nucleophilic character of the peroxo species responsible for the superior formation of sulfones: (1) nucleophilic parameter XNu = 0.92 in the oxidation of thianthrene 5-oxide and its decrease upon addition of acid; (2) sulfone to sulfoxide ratio of 24 in the competitive oxidation of methyl phenyl sulfoxide and p-Br-methyl phenyl sulfide; (3) significantly lower initial rates of methyl phenyl sulfide oxidation relative to methyl phenyl sulfoxide (kS/kSO = 0.05); and (4) positive slope ρ = +0.42 of the Hammett plot for competitive oxidation of p-substituted aryl methyl sulfoxides. Nucleophilic activation of H2O2 on Zr-MOF is also manifested by their capability of catalyzing epoxidation of electron-deficient C═C bonds in α,ß-unsaturated ketones accompanied by oxidation of acetonitrile solvent. Kinetic modeling on methyl phenyl sulfoxide oxidation coupled with adsorption studies supports a mechanism that involves the interaction of H2O2 with Zr sites with the formation of a nucleophilic oxidizing species and release of water followed by oxygen atom transfer from the nucleophilic oxidant to sulfoxide that competes with water for Zr sites. The nucleophilic peroxo species coexists with an electrophilic one, ZrOOH, capable of oxygen atom transfer to nucleophilic sulfides. The predominance of nucleophilic activation of H2O2 over electrophilic one is, most likely, ensured by the presence of weak basic sites in Zr-MOFs identified by FTIR spectroscopy of adsorbed CDCl3 and quantified by adsorption of isobutyric acid.