Preparation and application of multiple-component-doped keggin polyoxometalate microtubes--towards a component-tunable hollow structure

In this paper, the preparation of ascorbic acid (AA)-doped polyoxometalate (SiW(12)-AA) microtubes is described. The SiW(12)-AA microtubes convert to heteropoly blue microtubes upon exposure to ammonia gas, which is an ammonia-triggered solid-solid redox reaction between AA molecules and polyoxometalates, and can possibly be applied to a chemical sensor for detecting ammonia and volatile organic amines. Furthermore, the SiW(12)-AA microtubes have been applied to the in situ synthesis of Ag nanoparticles (NPs) through the redox reaction between the AA component and Ag(+) ions occurring on the surfaces of the SiW(12)-AA microtubes to give silver NPs immobilized on polyoxometalate microtubes (Ag@SiW(12)).     

Homogeneous catalysis by ruthenium carbonyl clusters

The historical background of and the incentive for using ruthenium carbonyl clusters as homogeneous catalysts are outlined. Keeping in view the possible solutions the uncertainties arising from declusterification and metal colloid formation are discussed. All ruthenium cluster-catalysed reactions are broadly classified as reactions with or without carbon monoxide as one of the reactants and the basic differences between such reactions are highlighted. Some of the factors of special relevance to cluster-catalysed reaction systems are mentioned. The reactions involving carbon monoxide are then discussed. These include water-gas-shift reaction, carbon monoxide hydrogenation, hydroformylation, reductive carbonylation of nitrobenzene and other carbonylation reactions. Hydrogenation, transfer hydrogenation, isomerisation and a few other reactions are then discussed. For all these reactions, special emphasis is laid on well-characterised cluster complexes that have been proposed as catalytic intermediates. Finally an attempt has been made to identify the path that future research in cluster catalysis is likely to follow.     

Unusual case of catalysis by palladium clusters

An unusual for Pd catalysts dehydration of α-alkyl and α, α′-dialkylbenzyl alcohols PhCR′R″OH (R′ = H, Me, Et, Bu; R″ = H, Me) occurs in the presence of the palladium(I) cluster [Pd₄(CO)₄(OAc)₄] (1) in an inert atmosphere to form ethers PhCR′R″-O-CR′ R″ and water. The catalyst is an intermediate of cluster 1 reduction to Pd black, while neither the starting cluster 1, nor Pd black, which is the decomposition product, are active in the catalysis of this reaction.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 788–791, March, 2005.     

Controllable self-assembly of organic-inorganic amphiphiles containing Dawson polyoxometalate clusters

An organic-inorganic molecular hybrid containing the Dawson polyoxometalate, ((C(4)H(9))(4)N)(5)H[P(2)V(3)W(15)O(59)(OCH(2))(3)CNHCOC(15)H(31)], was synthesized and its surfactant-like amphiphilic properties, represented by the formation of bilayer vesicles, were studied in polar solvents. The vesicle size decreases with both decreasing hybrid concentration and with increasing polarity of the solvent, independently. The self-assembly behavior of this hybrid can be controlled by introducing different counterions into the acetonitrile solutions. The addition of ZnCl(2) and NaI can cause a gradual decrease and increase of vesicular sizes, respectively. Tetraalkylammonium bromide is found to disassemble the vesicle assemblies. Moreover, the original counterions of the hybrid can be replaced with protons, resulting in pH-dependent formation of vesicles in aqueous solutions. The hybrid surfactant can further form micro-needle structures in aqueous solutions upon addition of Ca(2+) ions.     

Isolated and linear arrays of surfactant-encapsulated polyoxometalate clusters on graphite

We report on the self-assembly of several surfactant-encapsulated clusters (SECs) on the basal plane of graphite consisting of the doughnut-shaped tungstophosphate anion [Na(H2O)P5W30O110] covered by a hydrophobic shell of surfactants. Well-ordered rodlike structures are observed using scanning force microscopy. No such ordering is observed if the surfactant methyltrioctadecylammonium is used for encapsulation, suggesting that the density of alkyl chains around the polyoxometalate cluster is an important factor in determining the order of SEC assemblies on graphite. Coadsorption of tetratetracontane (n-C44H90) and (DODA)14[Na(H2O)P5W30O110] results in single, isolated SECs on a buffer layer of tetratetracontane, as determined by scanning tunneling microscopy.     

Micellar catalysis by perfluorooctanoic acid

Rates of acidic hydrolysis of hexano-, octano-, and decanohydroxamic acids and of 4-bromophenylaceto- and phenylacetohydroxamic acids have been determined in aqueous perfluorooctanoic acid—a reactive counterion surfactant system. Typical micellar catalysis was observed for the hydrolyses of the n-alkyl hydroxamic acids but not for the arylacetohydroxamic acids. The Arrhenius activation energy for hydrolysis of octano-hydroxamic acid is smaller above the cmc of the surfactant than it is below the cmc.     

Kinetic consequences of displacement adsorption in heterogeneous catalysis

Kinetic analysis of the simple reaction scheme of the heterogeneously catalyzed reaction AB has been made for the classical Langmuir adsorption and the Ipateev displacement adsorption. It has been shown that the only kinetic consequence of displacement adsorption is the different physical meaning of the parameters of the rate equation. Its form remains the same for both adsorption modes. This conclusion seems to be general also for other reaction schemes.

---

AB . , . . .

     

New trends in polyoxometalate photoredox chemistry: from photosensitisation to water oxidation catalysis

Molecular metal oxide clusters, so-called polyoxometalates (POM) have been extensively used as homogeneous photocatalysts in various photoredox reactions such as the oxidation of alkanes, alkenes and alcohols as well as the light-induced mineralisation of various organic and inorganic pollutants. The more general application of POMs as photoactive compounds, in particular in solar energy harnessing, has been hampered as the clusters typically absorb light in the UV-region only. Over the past decade, concepts have been put forward on how the reactivity of this class of compounds can be optimised to improve their overall photoactivity, and a particular focus has been on the design of photocatalytic processes which allow the conversion of solar light into useful chemical reactivity. This perspective gives a brief overview of general aspects of POM photochemistry and critically discusses the advantages and challenges of a range of POM-based systems for photooxidations and photoreductions with a focus on the development of sustainable solar light conversion systems.     

Mechanistic investigations of cooperative catalysis in the enantioselective fluorination of epoxides

This report describes mechanistic studies of the (salen)Co- and amine-cocatalyzed enantioselective ring opening of epoxides by fluoride. The kinetics of the reaction, as determined by in situ (19)F NMR analysis, are characterized by apparent first-order dependence on (salen)Co. Substituent effects, nonlinear effects, and reactivity with a linked (salen)Co catalyst provide evidence for a rate-limiting, bimetallic ring-opening step. To account for these divergent data, we propose a mechanism wherein the active nucleophilic fluorine species is a cobalt fluoride that forms a resting-state dimer. Axial ligation of the amine cocatalyst to (salen)Co facilitates dimer dissociation and is the origin of the observed cooperativity. On the basis of these studies, we show that significant improvements in the rates, turnover numbers, and substrate scope of the fluoride ring-opening reactions can be realized through the use of a linked salen framework. Application of this catalyst system to a rapid (5 min) fluorination to generate the unlabeled analog of a known PET tracer, F-MISO, is reported.     

Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters

Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O(2) pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption-desorption equilibrium was maintained. The virtual O(2) pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C-H and O═O activation steps. O* coverages and virtual pressures depend on O(2) pressure when O(2) activation is equilibrated and on O(2)/CH(4) ratios when this step becomes irreversible as a result of fast scavenging of O* by CH(4)-derived intermediates. In three of these kinetic regimes, C-H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen-oxygen (O*-O*), to oxygen-oxygen vacancy (O*-*), and to vacancy-vacancy (*-*) site pairs as O* coverages decrease. On O*-saturated cluster surfaces, O*-O* site pairs activate C-H bonds in CH(4) via homolytic hydrogen abstraction steps that form CH(3) groups with significant radical character and weak interactions with the surface at the transition state. In this regime, rates depend linearly on CH(4) pressure but are independent of O(2) pressure. The observed normal CH(4)/CD(4) kinetic isotope effects are consistent with the kinetic-relevance of C-H bond activation; identical (16)O(2)-(18)O(2) isotopic exchange rates in the presence or absence of CH(4) show that O(2) activation steps are quasi-equilibrated during catalysis. Measured and DFT-derived C-H bond activation barriers are large, because of the weak stabilization of the CH(3) fragments at transition states, but are compensated by the high entropy of these radical-like species. Turnover rates in this regime decrease with increasing Pt dispersion, because low-coordination exposed Pt atoms on small clusters bind O* more strongly than those that reside at low-index facets on large clusters, thus making O* less effective in H-abstraction. As vacancies (*, also exposed Pt atoms) become available on O*-covered surfaces, O*-* site pairs activate C-H bonds via concerted oxidative addition and H-abstraction in transition states effectively stabilized by CH(3) interactions with the vacancies, which lead to much higher turnover rates than on O*-O* pairs. In this regime, O(2) activation becomes irreversible, because fast C-H bond activation steps scavenge O* as it forms. Thus, O* coverages are set by the prevalent O(2)/CH(4) ratios instead of the O(2) pressures. CH(4)/CD(4) kinetic isotope effects are much larger for turnovers mediated by O*-* than by O*-O* site pairs, because C-H (and C-D) activation steps are required to form the * sites involved in C-H bond activation. Turnover rates for CH(4)-O(2) reactions mediated by O*-* pairs decrease with increasing Pt dispersion, as in the case of O*-O* active structures, because stronger O* binding on small clusters leads not only to less reactive O* atoms, but also to lower vacancy concentrations at cluster surfaces. As O(2)/CH(4) ratios and O* coverages become smaller, O(2) activation on bare Pt clusters becomes the sole kinetically relevant step; turnover rates are proportional to O(2) pressures and independent of CH(4) pressure and no CH(4)/CD(4) kinetic isotope effects are observed. In this regime, turnover rates become nearly independent of Pt dispersion, because the O(2) activation step is essentially barrierless. In the absence of O(2), alternate weaker oxidants, such as H(2)O or CO(2), lead to a final kinetic regime in which C-H bond dissociation on *-* pairs at bare cluster surfaces limit CH(4) conversion rates. Rates become first-order in CH(4) and independent of coreactant and normal CH(4)/CD(4) kinetic isotope effects are observed. In this case, turnover rates increase with increasing dispersion, because low-coordination Pt atoms stabilize the C-H bond activation transition states more effectively via stronger binding to CH(3) and H fragments. These findings and their mechanistic interpretations are consistent with all rate and isotopic data and with theoretical estimates of activation barriers and of cluster size effects on transition states. They serve to demonstrate the essential role of the coverage and reactivity of chemisorbed oxygen in determining the type and effectiveness of surface structures in CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants, as well as the diversity of rate dependencies, activation energies and entropies, and cluster size effects that prevail in these reactions. These results also show how theory and experiments can unravel complex surface chemistries on realistic catalysts under practical conditions and provide through the resulting mechanistic insights specific predictions for the effects of cluster size and surface coordination on turnover rates, the trends and magnitude of which depend sensitively on the nature of the predominant adsorbed intermediates and the kinetically relevant steps.     

Exploiting the multifunctionality of organocations in the assembly of hybrid polyoxometalate clusters and networks

Assembly of an unprecedented [(P(V)Mn(II)W(VI)(11)O(39))2{P(V)O(4)}](13-) and a [P(2)Mn(4)W(18)O(68)](10-) cluster have been observed and structurally characterised and cryospray mass spectroscopic ionization (CSI) has been used to observe one of the very reactive building blocks linking solid state with solution studies.     

Reaction cycles and poisoning in catalysis by gold clusters: A thermodynamics approach

In heterogeneous catalysis, a catalytic process takes place at finite temperature and at finite pressure of the atmosphere of the reactant gases. By applying ab initio atomistic thermodynamics to the model case of free Au₂ and clusters in an atmosphere of O₂ and CO, we derive all the thermodynamically possible reaction paths for the oxidation of CO to CO₂. This analysis lets us explain how gold clusters enable oxidation reactions without breaking the spin‐conservation rule. Furthermore, we identify special cluster + ligands compositions such as reaction intermediates and poisoned species. In particular, a thermodynamically driven poisoning is identified for the catalytic system containing free Au₂, and the experimental (p, T) conditions that avoid its formation are suggested. This implies that for some systems a catalytic cycle can be established, on thermodynamics grounds, only in a defined range of temperatures and pressures. In addition, our predictions for provide the so far most complete interpretation of the available experimental data (Socaciu et al, J. Am. Chem. Soc. 2003). © 2013 Wiley Periodicals, Inc.     

Sorting the assemblies of unsymmetrically covalently functionalized mn-anderson polyoxometalate clusters with mass spectrometry

The unsymmetrical Mn-Anderson polyoxometalate cluster, [N(C4H9)4]3[MnMo6O18(C4H6O3NO2)(C4H6O3NH2)] (1; N(C4H9)4(+) = TBA(+)), has been prepared and characterized by X-ray crystallography and electrospray ionization mass spectrometry (ESI-MS). Covalent functionalization of compound 1 leads to the controlled assemblies of unsymmetrical alkoxopolyoxometalate clusters of compounds 2-5, which can be directly observed in solution as revealed by ESI-MS studies.     

Mechanistic variations in the oxidation of Piloty's acid by metal complexes

The reactions of N-hydroxybenzenesulfonamide (Piloty's acid, PA) with a variety of metal oxidants are reported. Either nitric oxide or nitrite is the final reaction product, along with benzenesulfinate and the reduced metal compound. The nitrogen product depends on the oxidation potential of the metal oxidant and its ability to further oxidize NO to nitrite. The observation and preliminary interpretation of unusual kinetic behavior of Piloty's acid as a reductant is also described. Analogues of PA were also prepared and found to show similar reactivity.     

Design and analysis of chain and network structures from organic derivatives of polyoxometalate clusters

Polyoxometalate (POM) clusters derivatized with aniline groups exhibit distinct interactions with counterions and with each other. These interactions lead to the assembly of the clusters into chains and networks upon crystallization. Two cluster types were examined, [W(6)O(25)H(AsC(6)H(4)-4-NH(2))(2)](5-) and [Mo(12)O(46)(AsC(6)H(4)-4-NH(2))(4)](4-). The X-ray crystal structures were solved for the mixed salts containing [C(NH(2))(3)](+)/Na(+), Ag(+)/H(+), or Cu(2+)/H(+) as counterions. The X-ray crystal structures reveal that the POM clusters are linked together by hydrogen bonds or POM-metal ion-POM linkages. The roles of the counterions, solvents, and organic groups in the formation of specific crystalline architectures are discussed. Strongly interacting counterions form bonds to the oxo ligands of the POM and connect them into tetrameric units and/or into one-dimensional chains. The hydrogen bonding strength of the solvent influences the formation of hydrogen bonds between the aniline groups and oxo ligands of the cluster. The aniline groups played differing roles in the final structures: they were either nonbonding, bonded to a counterion, or involved in hydrogen bonding. Depending on the bonding interactions, the architecture of the cluster salts may be significantly altered.     

Micellar catalysis of oxidation of glycolic acid by N-bromophthalimide

Catalysis of oxidation of glycolic acid by N-bromophthalimide by micelles of cetyltrimethylammonium bromide (CTAB) at 318 K was investigated. The observed value of critical micelle concentration of CTAB in the presence of other components was lower than those reported in the literature. The oxidation reaction was strongly catalyzed by cationic micelles of CTAB. The reaction rate increased with CTAB concentration until the steady state was achieved. The reaction kinetics corresponded to first, fractional and inverse fiactional orders with respect to changes of concentration of reaction components. Effects of solvent, phthalimide, mercuric acetate, and potassium chloride on the reaction kinetics were also studied. The micelle-catalyzed oxidation reaction was shown to fit Arrhenius equation. The experimental data were rationalized in terms of Menger-Portnoy model considering a distribution of the reactants between the micellar and aqueous phases.