Catalytic Transfer Hydrogenation and Acid Reactions of Furfural and 5-(Hydroxymethyl)furfural over Hf-TUD-1 Type Catalysts.

Heterogeneous catalysis, which has served well the petrochemical industry, may valuably contribute towards a bio-based economy by sustainably enabling selective reactions to renewable chemicals. Carbohydrate-containing matter may be obtained from various widespread sources and selectively converted to furanic platform chemicals: furfural (Fur) and 5-(hydroxymethyl)furfural (Hmf). Valuable bioproducts may be obtained from these aldehydes via catalytic transfer hydrogenation (CTH) using alcohols as H-donors under relatively moderate reaction conditions. Hafnium-containing TUD-1 type catalysts were the first of ordered mesoporous silicates explored for the conversion of Fur and Hmf via CTH/alcohol strategies. The materials promoted CTH and acid reactions leading to the furanic ethers. The bioproducts spectrum was broader for the reaction of Fur than of Hmf. A Fur reaction mechanism based on literature data was discussed and supported by kinetic modelling. The influence of the Hf loading and reaction conditions (catalyst load, type of alcohol H-donor, temperature, initial substrate concentration) on the reaction kinetics was studied. The reaction conditions were optimized to maximize the yields of 2-(alkoxymethyl)furan ethers formed from Fur; up to 63% yield was reached at 88% Fur conversion, 4 h/150 °C, using Hf-TUD-1(75), which was a stable catalyst. The Hf-TUD-1(x) catalysts promoted the selective conversion of Hmf to bis(2-alkoxymethyl)furan; e.g., 96% selectivity at 98% Hmf conversion, 3 h/170 °C for Hf-TUD-1(50).

A Molybdenum Trioxide Hybrid Decorated by 3-(1,2,4-Triazol-4-yl)adamantane-1-carboxylic Acid: A Promising Reaction-Induced Self-Separating (RISS) Catalyst.

3-(1,2,4-Triazol-4-yl)adamantane-1-carboxylic acid (tradcH), a heterobifunctional organic ligand in which carboxylic acid and 1,2,4-triazole groups are united through a rigid 1,3-adamantanediyl spacer, was employed for the synthesis of a MoVI oxide organic hybrid. The ligand crystallized from water as tradcH·H2O (1), possessing a two-dimensional hydrogen-bonding network, and from ethanol as a cyclic molecular solvate with the composition (tradcH)3·2EtOH (2). Treatment of tradcH with MoO3 under hydrothermal conditions afforded a new Mo trioxide hybrid, [MoO3(tradcH)]·H2O (3), which was structurally characterized. In 3, the molybdenum atoms form a polymeric zigzag chain of {µ2-O-MoO2}n which is supported by double triazole bridges, while the carboxylic acid termini are left uncoordinated. The coordination environment of the Mo centers appears as distorted cis-{MoN2O4} octahedra. The hybrid exhibits high thermal stability (up to 270 °C) and was employed for a relatively broad scope of catalytic oxidation reactions in the liquid phase. Its catalytic behavior may be compared to a reversible mutation, featuring the best sides of homogeneous and heterogeneous catalysis. The original solid material converts into soluble active species, and the latter revert to the original material upon completion of the catalytic reaction, precipitating and allowing straightforward catalyst separation/reuse (like a heterogeneous catalyst). This catalyst was explored for a chemical reaction scope covering sulfoxidation, oxidative alcohol dehydrogenation, aldehyde oxidation, and olefin epoxidation, using hydrogen peroxide as an eco-friendly oxidant that gives water as a coproduct.

A Comparative Study of Molybdenum Carbonyl and Oxomolybdenum Derivatives Bearing 1,2,3-Triazole or 1,2,4-Triazoles in Catalytic Olefin Epoxidation.

The molybdenum(0)-carbonyl-triazole complexes [Mo(CO)3(L)3] [L = 1,2,3-triazole (1,2,3-trz) or 1,2,4-triazole (1,2,4-trz)] have been prepared and examined as precursors to molybdenum(VI) oxide catalysts for the epoxidation of cis-cyclooctene. Reaction of the carbonyl complexes with the oxidant tert-butyl hydroperoxide (TBHP) (either separately or in situ) gives oxomolybdenum(VI) hybrid materials that are proposed to possess one-dimensional polymeric structures in which adjacent oxo-bridged dioxomolybdenum(VI) moieties are further linked by bidentate bridging triazole (trz) ligands. A pronounced ligand influence on catalytic performance was found and the best result (quantitative epoxide yield within 1 h at 70 °C) was obtained with the 1,2,3-triazole oxomolybdenum(VI) hybrid. Both molybdenum oxide-triazole compounds displayed superior catalytic performance in comparison with the known hybrid materials [MoO3(trz)0.5], which have different structures based on organic-inorganic perovskite-like layers. With aqueous H2O2 as the oxidant instead of TBHP, all compounds were completely soluble and active. A pronounced ligand influence on catalytic performance was only found for the hybrids [MoO3(trz)0.5], and only the 1,2,4-trz compound displayed reaction-induced self-precipitation behavior. An insight into the type of solution species that may be involved in the catalytic processes with these compounds was obtained by separately treating [MoO3(1,2,4-trz)0.5] with excess H2O2, which led to the crystallization of the complex (NH4)1.8(H3O)0.2[Mo2O2(µ2-O)(O2)4(1,2,4-trz)]·H2O. The single-crystal X-ray investigation of this complex reveals an oxo-bridged dinuclear structure with oxodiperoxo groups being further linked by a single triazole bridge.

Triazolyl, Imidazolyl, and Carboxylic Acid Moieties in the Design of Molybdenum Trioxide Hybrids: Photophysical and Catalytic Behavior.

Three organic ligands bearing 1,2,4-triazolyl donor moieties, (S)-4-(1-phenylpropyl)-1,2,4-triazole (trethbz), 4-(1,2,4-triazol-4-yl)benzoic acid (trPhCO2H), and 3-(1H-imidazol-4-yl)-2-(1,2,4-triazol-4-yl)propionic acid (trhis), were prepared to evaluate their coordination behavior in the development of molybdenum(VI) oxide organic hybrids. Four compounds, [Mo2O6(trethbz)2]·H2O (1), [Mo4O12(trPhCO2H)2]·0.5H2O (2a), [Mo4O12(trPhCO2H)2]·H2O (2b), and [Mo8O25(trhis)2(trhisH)2]·2H2O (3), were synthesized and characterized. The monofunctional tr-ligand resulted in the formation of a zigzag chain [Mo2O6(trethbz)2] built up from cis-{MoO4N2} octahedra united through common µ2-O vertices. Employing the heterodonor ligand with tr/-CO2H functions afforded either layer or ribbon structures of corner- or edge-sharing {MoO5N} polyhedra (2a or 2b) stapled by tr-links in axial positions, whereas -CO2H groups remained uncoordinated. The presence of the im-heterocycle as an extra function in trhis facilitated formation of zwitterionic molecules with a protonated imidazolium group (imH+) and a negatively charged -CO2- group, whereas the tr-fragment was left neutral. Under the acidic hydrothermal conditions used, the organic ligand binds to molybdenum atoms either through [N-N]-tr or through both [N-N]-tr and µ2-CO2- units, which occur in protonated bidentate or zwitterionic tetradentate forms (trhisH+ and trhis, respectively). This leads to a new zigzag subtopological motif (3) of negatively charged polyoxomolybdate {Mo8O25}n2n- consisting of corner- and edge-sharing cis-{MoO4N2} and {MoO6} octahedra, while the tetradentate zwitterrionic trhis species connect these chains into a 2D net. Electronic spectra of the compounds showed optical gaps consistent with semiconducting behavior. The compounds were investigated as epoxidation catalysts via the model reactions of achiral and prochiral olefins (cis-cyclooctene and trans-ß-methylstyrene) with tert-butylhydroperoxide. The best-performing catalyst (1) was explored for the epoxidation of other olefins, including biomass-derived methyl oleate, methyl linoleate, and prochiral dl-limonene.

Robust Multifunctional Yttrium-Based Metal-Organic Frameworks with Breathing Effect.

Phosphonate- and yttrium-based metal-organic frameworks (MOFs), formulated as [Y(H5btp)]·5.5H2O (1), [Y(H5btp)]·2.5H2O (2), (H3O)[Y2(H5btp)(H4btp)]·H2O (3), and [Y(H5btp)]·H2O·0.5(MeOH) (4), were prepared using a "green" microwave-assisted synthesis methodology which promoted the self-assembly of the tetraphosphonic organic linker [1,1'-biphenyl]-3,3',5,5'-tetrayltetrakis(phosphonic acid) (H8btp) with Y3+ cations. This new family of functional materials, isolated in bulk quantities, exhibits a remarkable breathing effect. Structural flexibility was thoroughly studied by means of X-ray crystallography, thermogravimetry, variable-temperature X-ray diffraction, and dehydration and rehydration processes, ultimately evidencing a remarkable reversible single-crystal to single-crystal (SC-SC) transformation solely through the loss and gain of crystallization solvent molecules. Topologically, frameworks remained unaltered throughout this interconversion mechanism, with all compounds being binodal 6,6-connected network with a Schäfli symbol of {413.62}{48.66.8}. Results show that this is one of the most stable and thermally robust families of tetraphosphonate-based MOFs synthesized reported to date. Porous materials 2 and 3 were further studied to ascertain their performance as heterogeneous catalysts and proton conductors, respectively, with outstanding results being registered for both materials. Compound 2 showed a 94% conversion of benzaldehyde into (dimethoxymethyl)benzene after just 1 h of reaction, among the best results registered to date for MOF materials. On the other hand, the protonic conductivity of compound 3 at 98% of relative humidity (2.58 × 10-2 S cm-1) was among the highest registered among MOFs, with the great advantage of the material to be prepared using a simpler and sustainable synthesis methodology, as well as exhibiting a good stability at ambient conditions (temperature and humidity) over time when compared to others.

A Lamellar Coordination Polymer with Remarkable Catalytic Activity.

A positively charged lamellar coordination polymer based on a flexible triphosphonic acid linker is reported. [Gd(H4 nmp)(H2 O)2 ]Cl⋅2 H2 O (1) [H6 nmp=nitrilotris(methylenephosphonic acid)] was obtained by a one-pot approach by using water as a green solvent and by forcing the inclusion of additional acid sites by employing HCl in the synthesis. Compound 1 acts as a versatile heterogeneous acid catalyst with outstanding activity in organic reactions such as alcoholysis of styrene oxide, acetalization of benzaldehyde and cyclohexanaldehyde and ketalization of cyclohexanone. For all reaction systems, very high conversions were reached (92-97 %) in only 15-30 min under mild conditions (35 °C, atmospheric pressure). The coordination polymer exhibits a protonic conductivity of 1.23×10(-5)  S cm(-1) at 98 % relative humidity and 40 °C.

Catalytic alcoholysis of epoxides using metal-free cucurbituril-based solids.

Metal-free cucurbit[7]uril (CB7) solid-state assemblies promote acid-catalysed alcoholysis of aliphatic and aromatic epoxides under mild conditions to give ß-alkoxy alcohols, which are important intermediates for the synthesis of a vast range of compounds such as bioactive pharmaceuticals. The catalytic process is heterogeneous and the catalyst can be reused in consecutive runs without any reactivation treatment. The acid species responsible for the catalytic activity of CB7 may be entrapped hydronium ions.

Crystal Structure and Catalytic Behavior in Olefin Epoxidation of a One-Dimensional Tungsten Oxide/Bipyridine Hybrid.

The tungsten oxide/2,2'-bipyridine hybrid material [WO3(2,2'-bpy)]·nH2O (n = 1-2) (1) has been prepared in near quantitative yield by the reaction of H2WO4, 2,2'-bpy, and H2O in the mole ratio of ca. 1:2:700 at 160 °C for 98 h in a rotating Teflon-lined digestion bomb. The solid-state structure of 1 was solved and refined through Rietveld analysis of high-resolution synchrotron X-ray diffraction data collected for the microcrystalline powder. The material, crystallizing in the orthorhombic space group Iba2, is composed of a one-dimensional organic-inorganic hybrid polymer, ∞(1)[WO3(2,2'-bpy)], topologically identical to that found in the previously reported anhydrous phases [MO3(2,2'-bpy)] (M = Mo, W). While in the latter the N,N'-chelated 2,2'-bpy ligands of adjacent corner-shared {MO4N2} octahedra are positioned on the same side of the 1D chain, in 1 the 2,2'-bpy ligands alternate above and below the chain. The catalytic behavior of compound 1 for the epoxidation of cis-cyclooctene was compared with that for several other tungsten- or molybdenum-based (pre)catalysts, including the hybrid polymer [MoO3(2,2'-bpy)]. While the latter exhibits superior performance when tert-butyl hydroperoxide (TBHP) is used as the oxidant, compound 1 is superior when aqueous hydrogen peroxide is used, allowing near-quantitative conversion of the olefin to the epoxide. With H2O2, compounds 1 and [MoO3(2,2'-bpy)] act as sources of soluble active species, namely, the oxodiperoxo complex [MO(O2)2(2,2'-bpy)], which is formed in situ. Compounds 1 and [WO(O2)2(2,2'-bpy)] (2) were further tested in the epoxidation of cyclododecene, trans-2-octene, 1-octene, (R)-limonene, and styrene. The structure of 2 was determined by single-crystal X-ray diffraction and found to be isotypical with the molybdenum analogue.

Synthesis and Structural Elucidation of Triazolylmolybdenum(VI) Oxide Hybrids and Their Behavior as Oxidation Catalysts.

A large family of bifunctional 1,2,4-triazole molecular tectons (tr) has been explored for engineering molybdenum(VI) oxide hybrid solids. Specifically, tr ligands bearing auxiliary basic or acidic groups were of the type amine, pyrazole, 1H-tetrazole, and 1,2,4-triazole. The organically templated molybdenum(VI) oxide solids with the general compositions [MoO3(tr)], [Mo2O6(tr)], and [Mo2O6(tr)(H2O)2] were prepared under mild hydrothermal conditions or by refluxing in water. Their crystal structures consist of zigzag chains, ribbons, or helixes of alternating cis-{MoO4N2} or {MoO5N} polyhedra stapled by short [N-N]-tr bridges that for bitriazole ligands convert the motifs into 2D or 3D frameworks. The high thermal (235-350 °C) and chemical stability observed for the materials makes them promising for catalytic applications. The molybdenum(VI) oxide hybrids were successfully explored as versatile oxidation catalysts with tert-butyl hydroperoxide (TBHP) or aqueous H2O2 as an oxygen source, at 70 °C. Catalytic performances were influenced by the different acidic-basic properties and steric hindrances of coordinating organic ligands as well as the structural dimensionality of the hybrid.

Synthesis, structural elucidation, and catalytic properties in olefin epoxidation of the polymeric hybrid material [Mo3O9(2-[3(5)-pyrazolyl]pyridine)]n.

The reaction of [MoO2Cl2(pzpy)] (1) (pzpy = 2-[3(5)-pyrazolyl]pyridine) with water in an open reflux system (16 h), in a microwave synthesis system (120 °C, 2 h), or in a Teflon-lined stainless steel digestion bomb (100 °C, 19 h) gave the molybdenum oxide/pyrazolylpyridine polymeric hybrid material [Mo3O9(pzpy)]n (2) as a microcrystalline powder in yields of 72­79%. Compound 2 can also be obtained by the hydrothermal reaction of MoO3, pzpy, and H2O at 160 °C for 3 d. Secondary products isolated from the reaction solutions included the salt (pzpyH)2(MoCl4) (3) (pzpyH = 2-[3(5)-pyrazolyl]pyridinium), containing a very rare example of the tetrahedral MoCl4(2­) anion, and the tetranuclear compound [Mo4O12(pzpy)4] (4). Reaction of 2 with excess tert-butylhydroperoxide (TBHP) led to the isolation of the oxodiperoxo complex [MoO(O2)2(pzpy)] (5). Single-crystal X-ray structures of 3 and 5 are described. Fourier transform (FT)-IR and FT Raman spectra for 1, 4, and 5 were assigned based on density functional theory calculations. The structure of 2 was determined from synchrotron powder X-ray diffraction data in combination with other physicochemical information. In 2, a hybrid organic­inorganic one-dimensional (1D) polymer, ∞(1)[Mo3O9(pzpy)], is formed by the connection of two very distinct components: a double ladder-type inorganic core reminiscent of the crystal structure of MoO3 and 1D chains of corner-sharing distorted {MoO4N2} octahedra. Compound 2 exhibits moderate activity and high selectivity when used as a (pre)catalyst for the epoxidation of cis-cyclooctene with TBHP. Under the reaction conditions used, 2 is poorly soluble and is gradually converted into 5, which is at least partly responsible for the catalytic reaction.

Triazolyl-based copper-molybdate hybrids: from composition space diagram to magnetism and catalytic performance.

The multicomponent mixed-metal Cu(II)/Mo(VI) oxides/1,3-bis(1,2,4-triazol-4-yl)adamantane (tr2ad) system was thoroughly studied employing a compositional diagram approach. The concept allowed us to prepare three layered copper-molybdate hybrid solids [Cu(II)2(tr2ad)4](Mo8O26) (1), [Cu4(II)(µ4-O)(tr2ad)2(MoO4)3]·7.5H2O (2), and [Cu(I)2(tr2ad)2](Mo2O7)·H2O (3), and to elucidate the relationship between initial reagent concentration/stoichiometry and the stability of the resultant structural motifs. Compounds 1 and 2 were found to dominate throughout a wide crystallization range of the concentration triangle, whereas compound 3 was formed by redox processes in the narrow crystallization area having a high excess of Cu(OAc)2·H2O. Independent experiments carried out with Cu(OAc)2 and (NH4)6Mo7O24 in the absence of tr2ad, under the same conditions, revealed the formation of low-valent and bimetallic oxides, including Cu2O, MoO2, Cu(Mo3O10)·H2O, and Cu3(MoO4)2(OH)2. Compounds 1 and 2 show high thermal and chemical stability as examined as catalysts in the epoxidation of cis-cyclooctene and the oxidation of benzyl alcohol (BzOH) with different types of oxidants. The oxidation reaction of BzOH using tert-butyl hydroperoxide (TBHP) as the oxidant, in the presence of 1 or 2, led to benzaldehyde and benzoic acid (PhCO2H), with the latter being formed in up to 90% yield at 24 h. The results suggest that 1 and 2 may be favorable heterogeneous catalysts for the synthesis of PhCO2H. Whereas compound 1 only reveals a weak ferromagnetic coupling between neighboring Cu(II) centers (J = 0.41 cm(-1)), compound 2 shows distinct intracluster antiferromagnetic exchange interactions (J = -29.9 cm(-1), J' = -25.7 cm(-1)), which consequently results in a diamagnetic ground state.

Hydrothermal synthesis, crystal structure, and catalytic potential of a one-dimensional molybdenum oxide/bipyridinedicarboxylate hybrid.

The reaction of MoO3, 2,2'-bipyridine-5,5-dicarboxylic acid (H2bpdc), water, and dimethylformamide in the mole ratio 1:1:1730:130 at 150 °C for 3 days in a rotating Teflon-lined digestion bomb leads to the isolation of the molybdenum oxide/bipyridinedicarboxylate hybrid material (DMA)[MoO3(Hbpdc)]·nH2O (1) (DMA = dimethylammonium). Compound 1 was characterized by scanning electron microscopy, FT-IR and (13)C{(1)H} CP MAS NMR spectroscopies, and elemental and thermogravimetric analyses. The solid state structure of 1 was solved and refined through Rietveld analysis of high resolution synchrotron X-ray powder diffraction data in conjunction with information derived from the above techniques. The material, crystallizing in the noncentrosymmetric monoclinic space group Pc, is composed of an anionic one-dimensional organic-inorganic hybrid polymer, ∞(1)[MoO3(Hbpdc)](-), formed by corner-sharing distorted {MoO4N2} octahedra, which cocrystallizes with charge-balancing DMA(+) cations and one water molecule per metal center. In the crystal structure of 1, the close packing of individual anionic polymers, DMA(+) cations, and water molecules is mediated by a series of supramolecular contacts, namely strong (O-H···O, N(+)-H···O(-)) and weak (C-H···O) hydrogen bonding interactions, and π-π contacts involving adjacent coordinated Hbpdc(-) ligands. The catalytic potential of 1 was investigated in the epoxidation reactions of the bioderived olefins methyl oleate (Ole) and DL-limonene (Lim) using tert-butylhydroperoxide (TBHP) as the oxygen donor and 1,2-dichloroethane (DCE) or (trifluoromethyl)benzene (BTF) as cosolvent, at 55 or 75 °C. Under these conditions, 1 acts as a source of active soluble species, leading to epoxide yields of up to 98% for methyl 9,10-epoxystearate (BTF, 75 °C, 100% conversion of Ole) and 89% for 1,2-epoxy-p-menth-8-ene (DCE, 55 °C, 95% conversion of Lim). Catalytic systems employing the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide as solvent could be effectively recycled.

Single-Step Formation of Metal Oxide Nanostructures Wrapped in Mesoporous Silica and Silica-Niobia Catalysts for the Condensation of Furfural with Acetone.

The integration of metal oxide nanomaterials with mesoporous silica is a promising approach to exploiting the advantages of both types of materials. Traditional synthesis methods typically require multiple steps. This work instead presents a fast, one-step, template-free method for the synthesis of metal oxides homogeneously dispersed within mesoporous silica, including oxides of W, Ti, Nb, Ta, Sn, and Mo. These composites have tunable metal oxide contents, large surface areas, and wide mesopores. The combination of Nb2O5 nanoparticles (NPs) with SiO2 results in an increased surface area and a larger number of acid sites compared to pure Nb2O5 NPs. The surface texture and acidity of the silica-niobia composites can be tuned by adjusting the Nb/Si molar ratio. Moreover, the silica provides protection to the niobia NPs, preventing sintering during thermal treatment at 400 °C. The silica-niobia materials exhibit superior performance as catalysts in the aldol condensation of furfural (Fur) with acetone compared to pure niobia, leading to an up to 62% in product yield. Additionally, these catalysts show remarkable stability, retaining their performance over multiple runs. This work demonstrates the potential of the proposed synthesis approach for preparing more sustainable, high-performance, durable, and stable nanoscale metal oxide-based catalysts with a tunable composition, surface area, and active site density.

Tricarbonyl-Pyrazine-Molybdenum(0) Metal-Organic Frameworks for the Storage and Delivery of Biologically Active Carbon Monoxide.

Metal-organic frameworks (MOFs) have high potential as nanoplatforms for the storage and delivery of therapeutic gasotransmitters or gas-releasing molecules. The aim of the present study was to open an investigation into the viability of tricarbonyl-pyrazine-molybdenum(0) MOFs as carbon monoxide-releasing materials (CORMAs). A previous investigation found that the reaction of Mo(CO)6 with excess pyrazine (pyz) in a sealed ampoule gave a mixture comprising a major triclinic phase with pyz-occupied hexagonal channels, formulated as fac-Mo(CO)3(pyz)3/2·1/2pyz (Mo-hex), and a minor dense cubic phase, formulated as fac-Mo(CO)3(pyz)3/2 (Mo-cub). In the present work, an open reflux method in toluene has been optimized for the large-scale synthesis of the pure Mo-cub phase. The crystalline solids Mo-hex and Mo-cub were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), FT-IR and FT-Raman spectroscopies, and 13C{1H} cross-polarization (CP) magic-angle spinning (MAS) NMR spectroscopy. The release of CO from the MOFs was studied by the deoxy-myoglobin (deoxy-Mb)/carbonmonoxy-myoglobin (MbCO) UV-vis assay. Mo-hex and Mo-cub release CO upon contact with a physiological buffer in the dark, delivering 0.35 and 0.22 equiv (based on Mo), respectively, after 24 h, with half-lives of 3-4 h. Both materials display high photostability such that the CO-releasing kinetics is not affected by irradiation of the materials with UV light. These materials are attractive as potential CORMAs due to the slow release of a high CO payload. In the solid-state and under open air, Mo-cub underwent almost complete decarbonylation over a period of 4 days, corresponding to a theoretical CO release of 10 mmol per gram of material.

An octanuclear molybdenum(VI) complex containing coordinatively bound 4,4'-di-tert-butyl-2,2'-bipyridine, [Mo8O22(OH)4(di-tBu-bipy)4]: synthesis, structure, and catalytic epoxidation of bio-derived olefins.

The reaction of [MoO(2)Cl(2)(di-tBu-bipy)] (1) (di-tBu-bipy = 4,4'-di-tert-butyl-2,2'-bipyridine) with water at 100-120 °C in a Teflon-lined stainless steel autoclave, in an open reflux system, or in a microwave synthesis system gave the octanuclear complex [Mo(8)O(22)(OH)(4)(di-tBu-bipy)(4)] (2) as a microcrystalline powder in good yields. Single crystals of 2 suitable for X-ray diffraction were obtained by the reaction of MoO(3) and di-tBu-bipy in water at 160 °C for 3 days. The molecular structure of 2 comprises a purely inorganic core, Mo(4)O(8)(µ(3)-OH)(2)(µ(2)-O)(2), attached to two peripheral oxo-bridged binuclear units, Mo(2)O(4)(µ(2)-O)(2)(OH)(di-tBu-bipy)(2). The inorganic core is composed of a unique assembly of four {MoO(5)} distorted square pyramids connected to each other via edge-sharing. Overall, the octanuclear complex adopts a highly distorted form strongly resembling an "S"-shaped molecular unit. Complex 2 was applied in the catalytic epoxidation of the biorenewable olefins DL-limonene (Lim) and methyl oleate (Ole), using tert-butylhydroperoxide (TBHP) as an oxygen donor, under mild reaction conditions (55 °C, air). The reactions of Lim and Ole gave the respective epoxide monomers in fairly high selectivities at high conversions (89% 1,2-epoxy-p-menth-8-ene selectivity at 96% Lim conversion; 99% methyl 9,10-epoxystearate selectivity at 94% Ole conversion, reached within 24 h reaction). Iodometric titrations revealed no measurable "non-productive" decomposition of TBHP.

Synthesis, structural elucidation, and application of a pyrazolylpyridine-molybdenum oxide composite as a heterogeneous catalyst for olefin epoxidation.

The reaction of [MoO(2)Cl(2)(pypzEA)] (1) (pypzEA = ethyl[3-(pyridin-2-yl)-1H-pyrazol-1-yl]acetate) with water in a Teflon-lined stainless steel autoclave (100 °C) or in an open reflux system leads to the isolation of the molybdenum oxide/pyrazolylpyridine composite material [Mo(2)O(6)(HpypzA)] (2; HpypzA = [3-(pyridinium-2-yl)-1H-pyrazol-1-yl]acetate). The solid state structure of 2 was solved through single crystal and powder X-ray diffraction analyses in conjunction with information derived from FT-IR and (13)C CP MAS NMR spectroscopies and elemental analyses. In the asymmetric unit of 2, two crystallographically distinct Mo(6+) centers are bridged by a syn,syn-carboxylate group of HpypzA. The periodic repetition of these units along the a axis of the unit cell leads to the formation of a one-dimensional composite polymer, (∞)(1)[Mo(2)O(6)(HpypzA)]. The outstretched pyrazolylpyridine groups of adjacent polymers interdigitate to form a zipper-like motif, generating strong onset π-π contacts between adjacent rings of coordinated HpypzA molecules. The composite oxide 2 is a stable heterogeneous catalyst for liquid-phase olefin epoxidation.

Coupling of nanoporous chromium, aluminium-containing silicates with an ionic liquid for the transformation of glucose into 5-(hydroxymethyl)-2-furaldehyde.

Micro/mesoporous chromium, aluminium-containing silicates of the type TUD-1 (Al-TUD-1, Cr-TUD-1, CrAl-TUD-1) and zeolite BEA, Cr-BEA, and related composites BEA/TUD-1 and Cr-BEA/TUD-1, were prepared, characterised, and tested as solid acids coupled with the ionic liquid (IL) 1-butyl-3-methylimidazolium chloride ([bmim]Cl) as solvent, in the transformation of D-glucose into 5-(hydroxymethyl)-2-furaldehyde (Hmf), at 120 °C. The chromium-containing catalytic systems lead to considerably higher Hmf yields in comparison to the related systems without chromium. The IL is a favourable solvent for this target reaction (in terms of Hmf yields reached) compared to water or dimethylsulfoxide. A detailed study on the stabilities of the nanoporous solid acids in the IL medium is presented.

Micro/mesoporous LTL derived materials for catalytic transfer hydrogenation and acid reactions of bio-based levulinic acid and furanics.

The biomass-derived platform chemicals furfural and 5-(hydroxymethyl)furfural (HMF) may be converted to α-angelica lactone (AnL) and levulinic acid (LA). Presently, LA (synthesized from carbohydrates) has several multinational market players. Attractive biobased oxygenated fuel additives, solvents, etc., may be produced from AnL and LA via acid and reduction chemistry, namely alkyl levulinates and γ-valerolactone (GVL). In this work, hierarchical hafnium-containing multifunctional Linde type L (LTL) related zeotypes were prepared via top-down strategies, for the chemical valorization of LA, AnL and HMF via integrated catalytic transfer hydrogenation (CTH) and acid reactions in alcohol medium. This is the first report of CTH applications (in general) of LTL related materials. The influence of the post-synthesis treatments/conditions (desilication, dealumination, solid-state impregnation of Hf or Zr) on the material properties and catalytic performances was studied. AnL and LA were converted to 2-butyl levulinate (2BL) and GVL in high total yields of up to ca. 100%, at 200°C, and GVL/2BL molar ratios up to 10. HMF conversion gave mainly the furanic ethers 5-(sec-butoxymethyl)furfural and 2,5-bis(sec-butoxymethyl)furan (up to 63% total yield, in 2-butanol at 200°C/24 h). Mechanistic, reaction kinetics and material characterization studies indicated that the catalytic results depend on a complex interplay of different factors (material properties, type of substrate). The recovered-reused solids performed steadily.

Thermal transformation of a layered multifunctional network into a metal-organic framework based on a polymeric organic linker.

The preparation of layered [La(H(3)nmp)] as microcrystalline powders from optimized microwave-assisted synthesis or dynamic hydrothermal synthesis (i.e., with constant rotation of the autoclaves) from the reaction of nitrilotris(methylenephosphonic acid) (H(6)nmp) with LaCl(3)·7H(2)O is reported. Thermogravimetry in conjunction with thermodiffractometry showed that the material undergoes a microcrystal-to-microcrystal phase transformation above 300 °C, being transformed into either a three-dimensional or a two-dimensional network (two models are proposed based on dislocation of molecular units) formulated as [La(L)] (where L(3-) = [-(PO(3)CH(2))(2)(NH)(CH(2)PO(2))O(1/2)-](n)(3n-)). The two crystal structures were solved from ab initio methods based on powder X-ray diffraction data in conjunction with structural information derived from (13)C and (31)P solid-state NMR, electron microscopy (SEM and EDS mapping), FT-IR spectroscopy, thermodiffractometry, and photoluminescence studies. It is shown that upon heating the coordinated H(3)nmp(3-) anionic organic ligand undergoes a polymerization (condensation) reaction to form in situ a novel and unprecedented one-dimensional polymeric organic ligand. The lanthanum oxide layers act, thus, simultaneously as insulating and templating two-dimensional scaffolds. A rationalization of the various steps involved in these transformations is provided for the two models. Photoluminescent materials, isotypical with both the as-prepared ([(La(0.95)Eu(0.05))(H(3)nmp)] and [(La(0.95)Tb(0.05))(H(3)nmp)]) and the calcined ([(La(0.95)Eu(0.05))(L)]) compounds and containing stoichiometric amounts of optically active lanthanide centers, have been prepared and their photoluminescent properties studied in detail. The lifetimes of Eu(3+) vary between 2.04 ± 0.01 and 2.31 ± 0.01 ms (considering both ambient and low-temperature studies). [La(H(3)nmp)] is shown to be an effective heterogeneous catalyst in the ring opening of styrene oxide with methanol or ethanol, producing 2-methoxy-2-phenylethanol or 2-ethoxy-2-phenylethanol, respectively, in quantitative yields in the temperature range 40-70 °C. The material exhibits excellent regioselectivity to the ß-alkoxy alcohol products even in the presence of water. Catalyst recycling and leaching tests performed for [La(H(3)nmp)] confirm the heterogeneous nature of the catalytic reaction. Catalytic activity may be attributed to structural defect sites. This assumption is somewhat supported by the much higher catalytic activity of [La(L)] in comparison to [La(H(3)nmp)].