Selective isomerization of α-pinene oxide to campholenic aldehyde by ionic liquid-supported indenyl-molybdenum(II)-bipyridine complexes

Campholenic aldehyde (CPA), an important flavor and fragrance intermediate, can be obtained by the Lewis acid-catalyzed isomerization of α-pinene oxide (PinOx), although achieving high yields (>90%) is a difficult challenge due to the high reactivity of the epoxide. In the present work, indenyl-molybdenum(II)-bipyridine complexes [IndMo(bipyR)(CO)2](BF4) (bipyR = 2,2′-bipyridine (R = H) or 4,4′-disubstituted-2,2′-bipyridine) have been combined with various ionic liquid solvents to develop an efficient process for the selective conversion of PinOx to CPA under mild (35 °C) conditions. Excellent CPA yields (95%) were repeatedly obtained within 1 min reaction time for the easily recyclable catalytic system comprising [IndMo(4,4′-dinonyl-2,2′-bipyridine)(CO)2](BF4) and choline bis(trifluoromethylsulfonyl)imide.publishe

Synthesis and Characterization of Water Stable η3-Allyl Dicarbonyl Complexes of Molybdenum(II)

Trabalho apresentado nas VIII Jornadas CICECO, 18-19 de março 2011, Aveiro, PortugalN/

Intercalation of (η5-Pentamethylcyclopentadienyl)trioxomolybdenum(VI) in a Layered Double Hydroxide

A Zn,Al layered double hydroxide (LDH) with [Cp*MoO3]– (Cp* = η5‐C5Me5) anions in the interlayer has been prepared by a direct coprecipitation method. The intercalated LDH and the mixed metal oxide (MMO) obtained after its calcination were characterized by elemental and thermogravimetric analyses, powder X‐ray diffraction (PXRD), FT‐IR and FT‐Raman spectroscopy, 13C and 27Al MAS NMR, and scanning electron microscopy. The observed basal spacing of 17.1 Å for the LDH Zn,Al‐Cp*MoO3 (corresponding to a gallery height of 12.3 Å) suggests that the guest anions self‐assemble into dimers via offset face‐to‐face Cp*···Cp* interactions, which facilitates hydrogen‐bonding interactions between the oxido ligands of the complexes and the layer hydroxyl groups, while positioning the hydrophobic aromatic rings towards the center of the galleries. Calcination of Zn,Al‐Cp*MoO3 at 550 °C under air gave an MMO comprising well‐dispersed ZnO, α‐ZnMoO4 and ZnAl2O4 (spinel) oxides in a molar of ca. 1.4:1.6:1. The MMO exhibited catalytic activity for the epoxidation of cis‐cyclooctene with tert‐butylhydroperoxide (TBHP) as terminal oxidant, with quantitative yield of the epoxide being achieved within 24 h at 85 °C.publishe

Efficient isomerization of α-pinene oxide to campholenic aldehyde promoted by a mixed-ring analogue of molybdenocene

The MoIV complex [(eta5-indenyl)(eta5-cyclopentadienyl)Mo(MeCN)2](BF4)2 (1) has been used to promote two acid-catalyzed epoxide ring-opening reactions under ambient conditions. The alcoholysis of styrene oxide in neat ethanol gave 2-ethoxy-2-phenylethanol in quantitative yield within 10 min. The use of an ionic liquid (IL) as cosolvent benefitted catalyst solubility and recycling while not impairing catalytic performance. Complex 1 in 1,2-dichloroethane was effective for the isomerization of alpha-pinene oxide to campholenic aldehyde (CPA), leading to 87% yield at 1 h reaction. The same yield could be achieved within 1 min by using the IL [Choline][NTf2] as solvent. CPA yields at 1 min reached near-quantitative values (98%) upon recycling of the catalyst/IL mixture, demonstrating an unparalleled combination of activity, selectivity and recyclability for this commercially important reaction. Considering the catalytic features of the 1/IL system, a CPA process flow diagram is proposed and compared to patented technology.publishe

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.publishe

High-yield synthesis and catalytic response of chainlike hybrid materials of the [(MoO3)m(2,2′-bipyridine)n] family

The one-dimensional organic–inorganic hybrid material [MoO3(2,2'-bipy)] (1) (2,2'-bipy = 2,2'-bipyridine) has been used as a starting material to prepare the bipy-deficient phases [Mo2O6(2,2'-bipy)] (2) and [Mo3O9(2,2'-bipy)2] (3) in excellent yields. The hybrid 2 was obtained by a solid-state thermal treatment of 1 (300 ºC, 10 min) while 3 was obtained by a hydrothermal treatment of 1 (160 ºC, 6 d). A study was performed to compare the catalytic properties of 1–3 in the epoxidation of cis-cyclooctene at 55 ºC with tert-butylhydroperoxide (TBHP) or aqueous H2O2 as oxidant. In all cases Cy was converted to cyclooctene oxide (CyO) with 100% selectivity, and Cy conversions increased in the order 1 < 3 < 2, which parallels an increase in the Mo/2,20-bipy molar ratio of the hybrid (1 < 1.5 < 2). With compound 2, CyO yields at 24 h were 96% for TBHP (cosolvent a,a,a-trifluorotoluene) and 53% for H2O2 (cosolvent CH3CN). The catalytic reactions occurred in homogeneous phase with active species formed in situ from 1–3. All three hybrids react with aqueous H2O2 to give the catalytically active oxodiperoxo complex [MoO(O2)2(2,2'-bipy)]. The 2 : 1 hybrid 2 was further examined for the epoxidation of other cyclic and linear non-functionalised olefins with TBHP, namely cyclododecene, 1-octene and trans-2-octene, and the biomass-derived olefins DL-limonene, a-pinene and methyl oleate.publishe

Post-Synthesis Strategies to Prepare Mesostructured and Hierarchical Silicates for Liquid Phase Catalytic Epoxidation

Olefin epoxidation is an important transformation for the chemical valorization of olefins, which may derive from renewable sources or domestic/industrial waste. Different post-synthesis strategies were employed to introduce molybdenum species into mesostructured and hierarchical micro-mesoporous catalysts of the type TUD-1 and BEA, respectively, to confer epoxidation activity for the conversion of relatively bulky olefins (e.g., biobased methyl oleate, DL-limonene) to epoxide products, using tert-butyl hydroperoxide as an oxidant. The influences of (i) the type of metal precursor, (ii) type of post-synthesis impregnation method, (iii) type of support and (iv) top-down versus bottom-up synthesis methodologies were studied to achieve superior catalytic performances. Higher epoxidation activity was achieved for a material prepared via (post-synthesis) incipient wetness impregnation of MoO2(acac)2 (acac = acetylacetonate) on (pre-treated) siliceous TUD-1 and calcination; for example, methyl oleate was converted to the corresponding epoxide with 100% selectivity at 89% conversion (70 °C). Catalytic and solid-state characterization studies were conducted to shed light on material stability phenomena.publishe

Synthesis, Characterization and Catalytic application of Water Stable η3-Allyl Dicarbonyl Complexes of Molybdenum(II)

Trabalho apresentado em EuropaCat X – Catalysis across disciplines, 28 Aug - 02 Sep 2011, Glasgow, ScotlandN/

Desulfurization of liquid fuels by extraction and sulfoxidation using H2O2 and [CpMo(CO)3R] as catalysts

Efficient and recyclable liquid–liquid extraction and catalytic oxidative desulfurization (ECODS) systems for the removal of refractory sulfur compounds from liquid fuels are reported that use the cyclopentadienyl molybdenum tricarbonyl complexes [CpMo(CO)3Me] (1), [CpMo(CO)3(CH2-pC6H4-CO2Me] (2) and [CpMo(CO)3CH2COOH] (3) as catalyst precursors. An ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate, was used as both extractant and reaction medium, entrapping the active homogeneous MoVI catalysts that are formed in situ under the operating catalytic conditions (aqueous H2O2 as oxidant, 50 °C). The high sulfoxidation activity of the catalyst formed from 1 was largely responsible for enabling >99% desulfurization within 1 h of a model oil containing 1-benzothiophene, dibenzothiophene, 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene (2000 ppm S). The IL/catalyst phase could be repeatedly recycled with no loss of desulfurization efficiency. By sequentially performing extractive desulfurization and ECODS steps, 83–84% sulfur removal was achieved for untreated real diesel and jet fuel samples with initial sulfur contents of ca. 2300 and 1100 ppm, respectively.publishe

One-pot hydrogen production and cascade reaction of furfural to bioproducts over bimetallic Pd-Ni TUD-1 type mesoporous catalysts

Bimetallic Pd-Ni TUD-1 type mesoporous catalysts are effective for the cascade reaction of the renewable platform chemical furfural (FUR) to the useful bioproducts 2-alkoxyfuran, 2-methylfuran (2MF), 4-oxopentanal and its acetals, which find diverse applications, some already in the market. With a single catalyst, the in situ hydrogen supply from formic acid (FAc), as well as several acid-reduction steps of the overall catalytic process were triggered, leading to the desired bioproducts (bioPs), all in one-pot under moderate reaction conditions. These multipurpose materials were prepared using different procedures and conditions, which influenced the material properties and the catalytic performances. Detailed characterisation (microstructural/molecular level) and catalytic studies led to new mechanistic insights into the FUR reaction (with identification of intermediates), allowed to assess the roles of the different types of metal species in the complex reaction mechanism, understand the influence of material properties on the catalytic process, and catalyst stability and regeneration. The best-performing catalyst was prepared stepwise via impregnation of palladium on a hydrothermally synthesised nickel silicate with a molar ratio Si/Ni of 20, ending with filtration-washing-calcination procedures. This catalyst led to 83% 2MF yield, at 98% FUR conversion (90% total bioPs yield), using 1-butanol as solvent, at 170 °C. The reported catalytic protocol benefits from the fact that external usage of H2 for catalyst activation and/or the catalytic reaction is not required, no high-pressure gases are used, and FAc is used as source of hydrogen supplied in situ for the catalytic reaction under moderate conditions. Moreover, FAc presents low toxicity, it is easy to handle/store, and is a typical coproduct of carbohydrate biomass conversion processes, and thus its repurposing is highly desirable.publishe