Metal-Organic Frameworks as Heterogenous Photocatalysts for the Production of Solar Fuels

[ES] La presente tesis doctoral se ha basado en el estudio del uso de MOFs como fotocatalizadores para la producción de combustibles solares. Específicamente, los fotocatalizadores basados en MOF se han utilizado para la reacción de descomposición del agua y la reducción de CO2 en ausencia de agentes de sacrificio o disolventes orgánicos. MIL-125(Ti)-NH2 se puede utilizar como fotocatalizador para la reacción de descomposición del agua en presencia de UV-Vis o irradiación natural de la luz solar. La actividad de este material se puede potenciar mediante el uso de Pt y NPs de RuOx como co-catalizadores. Además, la actividad fotocatalítica de MIL 125(Ti)-NH2 se puede mejorar mediante un tratamiento de plasma de oxígeno que introduce defectos estructurales dando lugar a un material optimizado para catalizar la reacción de descomposición del agua. La presente tesis ha mostrado por primera vez la posibilidad de utilizar MOFs como fotocatalizadores para la metanación de CO2. En particular, un Zn-MOF y un Ti-MOF, MOF(Zn)-1 y MIP 208 respectivamente, se pueden utilizar como fotocatalizadores para promover la metanación de CO2 en condiciones de reacción suaves. Además, la actividad fotocatalítica de estos MOFs se incrementa en presencia de pequeñas NPs de Cu2O y, especialmente, por NPs de RuOx en la estructura de estos materiales. Es de destacar que el material compuesto por NPs de RuOx soportadas en MIL-125(Ti)-NH2 puede considerarse un fotocatalizador de referencia para la metanación de CO2 mediada por energía solar y en flujo continuo.[CA] La present tesi doctoral s'ha basat en l'estudi de l'ús de MOFs com a fotocatalitzadors per a la producció de combustibles solars. Específicament, els fotocatalitzadors basats en MOF s'han utilitzat per a la reacció de descomposició de l'aigua i la reducció de CO¿ en absència d'agents de sacrifici o dissolvents orgànics. MIL-125(Ti)-NH2 es pot utilitzar com fotocatalitzador per a la reacció de descomposició de l'aigua sota UV-Vis o irradiació natural de la llum solar i la seua activitat pot ser augmentada mitjançant l'ús de Pt i NPs de RuOx com co catalitzadors. A més, l'activitat fotocatalítica de MIL-125(Ti)-NH2 es pot millorar mitjançant un tractament de plasma d'oxigen que introdueix defectes estructurals resultant en un material optimitzat per a la reacció de descomposició de l'aigua. La present tesi ha mostrat per primera vegada la possibilitat d'utilitzar MOFs com fotocatalizador per a la metanació de CO¿. En particular, un Zn-MOF y un Ti MOF, MOF(Zn)-1 y MIP-208 respectivament, es poden utilitzar com fotocatalitzadors per a promoure la metanació de CO¿ en condicions de reacció suaus. A més, l'activitat fotocatalítica d'aquests MOFs pot ser realçada per la presència de xicotetes NPs de Cu2O i, especialment, per les NPs de RuOx en l'estructura d'aquestos materials. És de destacar que el material composat per NPs de RuOx suportades en MIL-125(Ti)-NH2 es pot considerar un fotocatalitzador de referència per a la metanació de CO2 amb energia solar i en flux continu.[EN] The present doctoral thesis studied the use of MOFs as photocatalysts to produce solar fuels. MOF-based photocatalysts were used for overall water splitting and CO2 reduction in the absence of sacrificial agents or organic solvents. MIL 125(Ti)-NH2 can be used as photocatalyst for overall water splitting under both UV-Vis or natural sunlight irradiation. The activity of this material can be enhanced using Pt and RuOx NPs as co-catalysts. Also, the photocatalytic activity of pristine MIL 125(Ti)-NH2 can be enhanced by oxygen-plasma treatment, which introduces structural defects and produces an optimized material for overall water splitting. This thesis has shown for the first time the possibility of using MOFs as photocatalysts for CO2 methanation. More specifically, a Zn and Ti MOF materials, MOF(Zn)-1 and MIP-208 respectively, can be used as photocatalysts to promote CO2 methanation under mild reaction conditions. The photocatalytic activity of these MOFs can be enhanced in the presence of small Cu2O NPs, and, especially, RuOx NPs in their structure. RuOx NPs supported on MIL-125(Ti)-NH2 can be envisioned as a benchmark photocatalyst for solar-driven CO2 methanation in continuous-flow operations.Cabrero Antonino, M. (2021). Metal-Organic Frameworks as Heterogenous Photocatalysts for the Production of Solar Fuels [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/17666

Reacciones de hidroadición regioselectiva sobre alquenos y alquinos catalizadas por triflimida de hierro (III)

En la presente tesis se ha estudiado el comportamiento catalítico de la especie triflimida de hierro(III), de fórmula Fe(NTf2)3 donde (Tf = SO2CF3), para una serie de reacciones de hidroadición regioselectiva sobre alquenos y alquinos. Esta sal metálica constituida por un catión con carácter ácido duro de Lewis (Fe3+) junto con un anión poco coordinante y de baja nucleofília como el (-NTf2) ha demostrado ser un catalizador altamente eficiente para la activación de enlaces múltiples C-C (alquenos y alquinos). En todas estas reacciones se observa una buena regioselectividad hacia posiciones bencílicas (posición interna del doble enlace en estirenos y del triple enlace en fenilacetilenos). El catalizador Fe(NTf2)3 se genera de manera sencilla y directa en 1,4-dioxano a partir de la reacción de metátesis entre FeCl3 y AgNTf2, y su formación y naturaleza química se han estudiado por estudios de espectroscopia RMN de 19F y 15N, voltamperometría cíclica, espectroscopia UV-VIS y resonancia paramagnética electrónica (RPE). La presencia de aniones triflimida genera, en principio, una estabilización del LUMO del hierro (orbitales 3d), lo que le confiere un mayor carácter electropositivo y aumentan por tanto su acidez de Lewis. Adicionalmente, la triflimida de hierro(III) presenta una configuración electrónica de alto espín, teniendo los 5 electrones 3d del hierro(III) desapareados en configuración de capa semillena. Las principales reacciones estudiadas donde la triflimida de hierro(III) es un catalizador activo y selectivo son: 1) dimerización cabeza-cola de estirenos para obtener olefinas sustituidas, 2) hidrotiolación regioselectiva en posición Markovnikov de estirenos para obtener tioéteres bencílicos y 3) hidratación regioselectiva en posición Markovnikov de alquinos para obtener cetonas. El hierro(III) en forma de Fe(NTf2)3 y sin ayuda de ligando auxiliar, puede actuar como un catalizador sustituto del complejo de oro(I) de fórmula PPh3AuNTf2 para una serie de reacciones de hidroadición regioselectiva sobre alquenos y alquinos. Mediante estudios in-situ de espectroscopia RMN de 19F, 15N y 31P se ha demostrado que en determinadas condiciones de reacción (temperatura, reactivos y disolvente adecuados) el complejo PPh3AuNTf2 es inestable y puede sufrir cierta hidrólisis parcial generando in-situ ácido triflimídico (HNTf2), mientras que Fe(NTf2)3 se mantiene estable.Cabrero Antonino, JR. (2013). Reacciones de hidroadición regioselectiva sobre alquenos y alquinos catalizadas por triflimida de hierro (III) [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/34673TESISPremiad

Catalytic Reductive N-Alkylations Using CO2 and Carboxylic Acid Derivatives: Recent Progress and Developments

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The safety, easy accessibility, and high stability of these reagents makes the development of new reductive transformations with them as N-alkylating agents a useful alternative to existing procedures. In this Review, we summarize reported examples of one-pot reductive N-alkylation methods that use carboxylic/carbonic acid derivatives or CO2 as alkylating agents.This work was supported by the state of MecklenburgVorpommern and the BMBF. J.R.C.-A. thanks the Ministerio de Ciencia, Innovacion y Universidades for a Juan de la Cierva contract. R.A. thanks UPV for a postdoctoral contract.Cabrero Antonino, JR.; Adam-Ortiz, R.; Beller, M. (2019). Catalytic Reductive N-Alkylations Using CO2 and Carboxylic Acid Derivatives: Recent Progress and Developments. Angewandte Chemie International Edition. 58(37):12820-12838. https://doi.org/10.1002/anie.201810121S12820128385837Adams, J. M., & Cory, S. (1975). Modified nucleosides and bizarre 5′-termini in mouse myeloma mRNA. 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Journal of the American Chemical Society, 126(23), 7368-7377. doi:10.1021/ja048557sHollmann, D., Bähn, S., Tillack, A., & Beller, M. (2007). A General Ruthenium-Catalyzed Synthesis of Aromatic Amines. Angewandte Chemie International Edition, 46(43), 8291-8294. doi:10.1002/anie.200703119Hollmann, D., Bähn, S., Tillack, A., & Beller, M. (2007). Eine allgemeine rutheniumkatalysierte Synthese von aromatischen Aminen. Angewandte Chemie, 119(43), 8440-8444. doi:10.1002/ange.200703119Hollmann, D., Bähn, S., Tillack, A., & Beller, M. (2008). N-Dealkylation of aliphatic amines and selective synthesis of monoalkylated aryl amines. Chemical Communications, (27), 3199. doi:10.1039/b803114bSaidi, O., Blacker, A. J., Farah, M. M., Marsden, S. P., & Williams, J. M. J. (2009). Selective Amine Cross-Coupling Using Iridium-Catalyzed «Borrowing Hydrogen» Methodology. Angewandte Chemie International Edition, 48(40), 7375-7378. doi:10.1002/anie.200904028Saidi, O., Blacker, A. J., Farah, M. M., Marsden, S. P., & Williams, J. M. J. (2009). Selective Amine Cross-Coupling Using Iridium-Catalyzed «Borrowing Hydrogen» Methodology. Angewandte Chemie, 121(40), 7511-7514. doi:10.1002/ange.200904028Guillena, G., Ramón, D. J., & Yus, M. (2009). Hydrogen Autotransfer in theN-Alkylation of Amines and Related Compounds using Alcohols and Amines as Electrophiles. Chemical Reviews, 110(3), 1611-1641. doi:10.1021/cr9002159Zhao, Y., Foo, S. W., & Saito, S. (2011). Iron/Amino Acid Catalyzed Direct N-Alkylation of Amines with Alcohols. Angewandte Chemie International Edition, 50(13), 3006-3009. doi:10.1002/anie.201006660Zhao, Y., Foo, S. W., & Saito, S. (2011). Iron/Amino Acid Catalyzed Direct N-Alkylation of Amines with Alcohols. Angewandte Chemie, 123(13), 3062-3065. doi:10.1002/ange.201006660Bähn, S., Imm, S., Neubert, L., Zhang, M., Neumann, H., & Beller, M. (2011). The Catalytic Amination of Alcohols. ChemCatChem, 3(12), 1853-1864. doi:10.1002/cctc.201100255Abarca, B., Adam, R., & Ballesteros, R. (2012). An efficient one pot transfer hydrogenation and N-alkylation of quinolines with alcohols mediated by Pd/C/Zn. Organic & Biomolecular Chemistry, 10(9), 1826. doi:10.1039/c1ob05888fYang, Q., Wang, Q., & Yu, Z. (2015). Substitution of alcohols by N-nucleophiles via transition metal-catalyzed dehydrogenation. Chemical Society Reviews, 44(8), 2305-2329. doi:10.1039/c4cs00496eYin, Z., Zeng, H., Wu, J., Zheng, S., & Zhang, G. (2016). Cobalt-Catalyzed Synthesis of Aromatic, Aliphatic, and Cyclic Secondary Amines via a «Hydrogen-Borrowing» Strategy. ACS Catalysis, 6(10), 6546-6550. doi:10.1021/acscatal.6b02218Arachchige, P. T. K., Lee, H., & Yi, C. S. (2018). Synthesis of Symmetric and Unsymmetric Secondary Amines from the Ligand-Promoted Ruthenium-Catalyzed Deaminative Coupling Reaction of Primary Amines. The Journal of Organic Chemistry, 83(9), 4932-4947. doi:10.1021/acs.joc.8b00649Müller, T. E., & Beller, M. (1998). Metal-Initiated Amination of Alkenes and Alkynes†. Chemical Reviews, 98(2), 675-704. doi:10.1021/cr960433dBeller, M., Seayad, J., Tillack, A., & Jiao, H. (2004). Catalytic Markovnikov and anti-Markovnikov Functionalization of Alkenes and Alkynes: Recent Developments and Trends. Angewandte Chemie International Edition, 43(26), 3368-3398. doi:10.1002/anie.200300616Beller, M., Seayad, J., Tillack, A., & Jiao, H. (2004). Katalytische Markownikow- und Anti-Markownikow-Funktionalisierung von Alkenen und Alkinen. Angewandte Chemie, 116(26), 3448-3479. doi:10.1002/ange.200300616Müller, T. E., Hultzsch, K. C., Yus, M., Foubelo, F., & Tada, M. (2008). Hydroamination: Direct Addition of Amines to Alkenes and Alkynes. Chemical Reviews, 108(9), 3795-3892. doi:10.1021/cr0306788Leyva-Pérez, A., Cabrero-Antonino, J. R., Cantín, A., & Corma, A. (2010). Gold(I) Catalyzes the Intermolecular Hydroamination of Alkynes with Imines and Produces α,α′,N-Triarylbisenamines: Studies on Their Use As Intermediates in Synthesis. The Journal of Organic Chemistry, 75(22), 7769-7780. doi:10.1021/jo101674tYim, J. C.-H., & Schafer, L. L. (2014). Efficient Anti-Markovnikov-Selective Catalysts for Intermolecular Alkyne Hydroamination: Recent Advances and Synthetic Applications. European Journal of Organic Chemistry, 2014(31), 6825-6840. doi:10.1002/ejoc.201402300Gui, J., Pan, C.-M., Jin, Y., Qin, T., Lo, J. C., Lee, B. J., … Baran, P. S. (2015). Practical olefin hydroamination with nitroarenes. Science, 348(6237), 886-891. doi:10.1126/science.aab0245Huang, L., Arndt, M., Gooßen, K., Heydt, H., & Gooßen, L. J. (2015). Late Transi

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

Catalytic hydrogenation of amides is of great interest for chemists working in organic synthesis, as the resulting amines are widely featured in natural products, drugs, agrochemicals, dyes, etc. Compared to traditional reduction of amides using (over)stoichiometric reductants, the direct hydrogenation of amides using molecular hydrogen represents a greener approach. Furthermore, amide hydrogenation is a highly versatile transformation, since not only higher amines (obtained by C–O cleavage), but also lower amines and alcohols, or amino alcohols (obtained by C–N cleavage) can be selectively accessed by fine tuning of reaction conditions. This review describes the most recent advances in the area of amide hydrogenation using H2 exclusively and molecularly defined homogeneous as well as nano-structured heterogeneous catalysts, with a special focus on catalyst development and synthetic applications

Gold(I) catalyses the intermolecular hydroenamination of alkynes with imines and produces alfa,alfa',N-triarylbisenamines: studies on their use as intermediates in synthesis

[EN] alpha,alpha',N-Tnarylbisenamines have been efficiently formed and isolated for the first time The synthesis is based on an unprecedented gold(I)-catalyzed double intermolecular hydroamination between N-arylamines and aryl alkynes This reaction constitutes a new example of the intriguing behavior of gold as catalyst in organic synthesis The reactivity of these bisenamines for three different reactions, leading to potentially useful intermediates, is also shown In particular, hindered azabicycles [3 2 0], which present excellent UVA and UVB absorption properties, are obtained by addition of triarylbisenamines to propiolates following an unexpected mechanismThis work is dedicated to Prof Steven V Ley on the occasion of his 65th birthday A L-P thanks CSIC for a contract under the JAE-doctors program Financial support by the PLE2009 project form MCIINN and PRO-METEO from Generalitat Valenciana are also acknowledged We thank Dr I Andreu for discussions on UV results The Continuous support from the ITQ's NMR team is also particularly appreciatedLeyva Perez, A.; Cabrero Antonino, JR.; Cantin Sanz, A.; Corma Canós, A. (2010). Gold(I) catalyses the intermolecular hydroenamination of alkynes with imines and produces alfa,alfa',N-triarylbisenamines: studies on their use as intermediates in synthesis. The Journal of Organic Chemistry. 75(22):7769-7780. doi:10.1021/jo101674tS77697780752

Reductive N-methylation of amines using dimethyl carbonate and molecular hydrogen: Mechanistic insights through kinetic modelling

[EN] Kinetic analysis of ruthenium-catalyzed reductive N-methylation of amines using dimethyl carbonate as C1 source and molecular hydrogen as reductant has been performed. Kinetic equations have been derived and kinetic modelling has been performed for experimental data generated previously at a constant hydrogen pressure as well as for additional experiments performed at different hydrogen pressures. The study has revealed interesting kinetic features related to an induction period strongly influenced by temperature. A kinetic model has been proposed based on advanced reaction mechanism featuring transformation between different type of catalytic species and inactivation of them during the reaction. Kinetic modelling was done for all data sets together showing excellent correspondence between calculations and experiments.Cabrero Antonino, JR.; Adam-Ortiz, R.; Wärnå, J.; Murzin, DY.; Beller, M. (2018). Reductive N-methylation of amines using dimethyl carbonate and molecular hydrogen: Mechanistic insights through kinetic modelling. Chemical Engineering Journal. 351:1129-1136. https://doi.org/10.1016/j.cej.2018.06.174S1129113635

Tuning the Microenvironment of Gold Nanoparticles Encapsulated within MIL-101(Cr) for the Selective Oxidation of Alcohols with O-2: Influence of the Amino Terephthalate Linker

This is the peer reviewed version of the following article: Chem. Eur. J. 2019, 25, 9280 9286, which has been published in final form at https://doi.org/10.1002/chem.201901361. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] This manuscript reports a comparative study of the catalytic performance of gold nanoparticles (NPs) encapsulated within MIL-101(Cr) with or without amino groups in the terephthalate linker. The purpose is to show how the amino groups can influence the microenvironment and catalytic stability of incorporated gold nanoparticles. The first influence of the presence of this substituent is the smaller particle size of Au NPs hosted in MIL-101(Cr)-NH2 (2.45 +/- 0.19 nm) compared with the parent MIL-101(Cr)-H (3.02 +/- 0.39 nm). Both materials are highly active to promote the aerobic alcohol oxidation and exhibit a wide substrate scope. Although both catalysts can achieve turnover numbers as high as 10(6) for the solvent-free aerobic oxidation of benzyl alcohol, Au@MIL-101(Cr)-NH2 exhibits higher turnover frequency values (12 000 h(-1)) than Au@MIL-101(Cr)-H (6800 h(-1)). Au@MIL-101(Cr)-NH2 also exhibits higher catalytic stability, being recyclable for 20 times with coincident temporal conversion profiles, in comparison with some decay observed in the parent Au@MIL-101(Cr)-H. Characterization by transmission electron microscopy of the 20-times used samples shows a very minor particle size increase in the case of Au@MIL-101(Cr)-NH2 (2.97 +/- 0.27 nm) in comparison with the Au@MIL-101(Cr)-H analog (5.32 +/- 0.72 nm). The data presented show the potential of better control of the microenvironment to improve the performance of encapsulated Au nanoparticles.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa, CTQ2015-65963-CQ-R1 and CTQ2014-53292-R) is gratefully acknowledged. Generalidad Valenciana is also thanked for funding (Prometeo 2017/083). S.N. thanks financial support by the Fundacijn Ramjn Areces (XVIII Concurso Nacional para la Adjudicacijn de Ayudas a la Investigacijn en Ciencias de la Vida y de la Materia, 2016).Santiago-Portillo, A.; Cabrero-Antonino, M.; Alvaro Rodríguez, MM.; Navalón Oltra, S.; García Gómez, H. (2019). Tuning the Microenvironment of Gold Nanoparticles Encapsulated within MIL-101(Cr) for the Selective Oxidation of Alcohols with O-2: Influence of the Amino Terephthalate Linker. Chemistry - A European Journal. 25(39):9280-9286. https://doi.org/10.1002/chem.201901361S928092862539H�ft, E., Kosslick, H., Fricke, R., & Hamann, H.-J. (1996). Titanhaltige Molekularsiebe als Katalysatoren f�r selektive Oxidationsreaktionen mit Wasserstoffperoxid. Journal f�r Praktische Chemie/Chemiker-Zeitung, 338(1), 1-15. doi:10.1002/prac.19963380102Matsumoto, T., Ueno, M., Wang, N., & Kobayashi, S. (2008). Recent Advances in Immobilized Metal Catalysts for Environmentally Benign Oxidation of Alcohols. Chemistry - An Asian Journal, 3(2), 196-214. doi:10.1002/asia.200700359Saikia, M., Bhuyan, D., & Saikia, L. (2015). Facile synthesis of Fe3O4nanoparticles on metal organic framework MIL-101(Cr): characterization and catalytic activity. New Journal of Chemistry, 39(1), 64-67. doi:10.1039/c4nj01312cCorma, A., & Garcia, H. (2008). Supported gold nanoparticles as catalysts for organic reactions. Chemical Society Reviews, 37(9), 2096. doi:10.1039/b707314nParmeggiani, C., & Cardona, F. (2012). Transition metal based catalysts in the aerobic oxidation of alcohols. Green Chemistry, 14(3), 547. doi:10.1039/c2gc16344fStahl, S. S. (2004). Palladium Oxidase Catalysis: Selective Oxidation of Organic Chemicals by Direct Dioxygen-Coupled Turnover. Angewandte Chemie International Edition, 43(26), 3400-3420. doi:10.1002/anie.200300630Dhakshinamoorthy, A., & Garcia, H. (2012). Catalysis by metal nanoparticles embedded on metal–organic frameworks. Chemical Society Reviews, 41(15), 5262. doi:10.1039/c2cs35047eAlhumaimess, M., Lin, Z., He, Q., Lu, L., Dimitratos, N., Dummer, N. F., … Hutchings, G. J. (2014). Oxidation of Benzyl Alcohol and Carbon Monoxide Using Gold Nanoparticles Supported on MnO2Nanowire Microspheres. Chemistry - A European Journal, 20(6), 1701-1710. doi:10.1002/chem.201303355Buonerba, A., Cuomo, C., Ortega Sánchez, S., Canton, P., & Grassi, A. (2011). Gold Nanoparticles Incarcerated in Nanoporous Syndiotactic Polystyrene Matrices as New and Efficient Catalysts for Alcohol Oxidations. Chemistry - A European Journal, 18(2), 709-715. doi:10.1002/chem.201101034Costa, V. V., Estrada, M., Demidova, Y., Prosvirin, I., Kriventsov, V., Cotta, R. F., … Gusevskaya, E. V. (2012). Gold nanoparticles supported on magnesium oxide as catalysts for the aerobic oxidation of alcohols under alkali-free conditions. Journal of Catalysis, 292, 148-156. doi:10.1016/j.jcat.2012.05.009Zhang, W., Xiao, Z., Wang, J., Fu, W., Tan, R., & Yin, D. (2019). Selective Aerobic Oxidation of Alcohols over Gold‐Palladium Alloy Catalysts Using Air at Atmospheric Pressure in Water. ChemCatChem, 11(6), 1779-1788. doi:10.1002/cctc.201900015Liu, X. Y., Wang, A., Zhang, T., & Mou, C.-Y. (2013). Catalysis by gold: New insights into the support effect. Nano Today, 8(4), 403-416. doi:10.1016/j.nantod.2013.07.005Navalon, S., Dhakshinamoorthy, A., Alvaro, M., & Garcia, H. (2016). Metal nanoparticles supported on two-dimensional graphenes as heterogeneous catalysts. Coordination Chemistry Reviews, 312, 99-148. doi:10.1016/j.ccr.2015.12.005Dhakshinamoorthy, A., Asiri, A. M., & Garcia, H. (2017). Metal Organic Frameworks as Versatile Hosts of Au Nanoparticles in Heterogeneous Catalysis. ACS Catalysis, 7(4), 2896-2919. doi:10.1021/acscatal.6b03386Howarth, A. J., Liu, Y., Li, P., Li, Z., Wang, T. C., Hupp, J. T., & Farha, O. K. (2016). Chemical, thermal and mechanical stabilities of metal–organic frameworks. Nature Reviews Materials, 1(3). doi:10.1038/natrevmats.2015.18Lee, J., Farha, O. K., Roberts, J., Scheidt, K. A., Nguyen, S. T., & Hupp, J. T. (2009). Metal–organic framework materials as catalysts. Chemical Society Reviews, 38(5), 1450. doi:10.1039/b807080fLeus, K., Concepcion, P., Vandichel, M., Meledina, M., Grirrane, A., Esquivel, D., … Van Der Voort, P. (2015). Au@UiO-66: a base free oxidation catalyst. RSC Advances, 5(29), 22334-22342. doi:10.1039/c4ra16800cSaikia, M., Kaichev, V., & Saikia, L. (2016). Gold nanoparticles supported on nanoscale amine-functionalized MIL-101(Cr) as a highly active catalyst for epoxidation of styrene. RSC Advances, 6(108), 106856-106865. doi:10.1039/c6ra24458kLiu, H., Liu, Y., Li, Y., Tang, Z., & Jiang, H. (2010). Metal−Organic Framework Supported Gold Nanoparticles as a Highly Active Heterogeneous Catalyst for Aerobic Oxidation of Alcohols. The Journal of Physical Chemistry C, 114(31), 13362-13369. doi:10.1021/jp105666fLammert, M., Bernt, S., Vermoortele, F., De Vos, D. E., & Stock, N. (2013). Single- and Mixed-Linker Cr-MIL-101 Derivatives: A High-Throughput Investigation. Inorganic Chemistry, 52(15), 8521-8528. doi:10.1021/ic4005328Zhu, Q.-L., Li, J., & Xu, Q. (2013). Immobilizing Metal Nanoparticles to Metal–Organic Frameworks with Size and Location Control for Optimizing Catalytic Performance. Journal of the American Chemical Society, 135(28), 10210-10213. doi:10.1021/ja403330mChen, Y. F., Babarao, R., Sandler, S. I., & Jiang, J. W. (2010). Metal−Organic Framework MIL-101 for Adsorption and Effect of Terminal Water Molecules: From Quantum Mechanics to Molecular Simulation. Langmuir, 26(11), 8743-8750. doi:10.1021/la904502hFerey, G. (2005). A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area. Science, 309(5743), 2040-2042. doi:10.1126/science.1116275Santiago-Portillo, A., Navalón, S., Cirujano, F. G., Xamena, F. X. L. i, Alvaro, M., & Garcia, H. (2015). MIL-101 as Reusable Solid Catalyst for Autoxidation of Benzylic Hydrocarbons in the Absence of Additional Oxidizing Reagents. ACS Catalysis, 5(6), 3216-3224. doi:10.1021/acscatal.5b00411Buxton, G. V., Greenstock, C. L., Helman, W. P., & Ross, A. B. (1988). Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O− in Aqueous Solution. Journal of Physical and Chemical Reference Data, 17(2), 513-886. doi:10.1063/1.555805Clifton, C. L., & Huie, R. E. (1989). Rate constants for hydrogen abstraction reactions of the sulfate radical, SO4?. Alcohols. International Journal of Chemical Kinetics, 21(8), 677-687. doi:10.1002/kin.550210807Dhakshinamoorthy, A., Asiri, A. M., & Garcia, H. (2017). Tuneable nature of metal organic frameworks as heterogeneous solid catalysts for alcohol oxidation. Chemical Communications, 53(79), 10851-10869. doi:10.1039/c7cc05927bCancino, P., Vega, A., Santiago-Portillo, A., Navalon, S., Alvaro, M., Aguirre, P., … García, H. (2016). A novel copper(ii)–lanthanum(iii) metal organic framework as a selective catalyst for the aerobic oxidation of benzylic hydrocarbons and cycloalkenes. Catalysis Science & Technology, 6(11), 3727-3736. doi:10.1039/c5cy01448dGómez-Paricio, A., Santiago-Portillo, A., Navalón, S., Concepción, P., Alvaro, M., & Garcia, H. (2016). MIL-101 promotes the efficient aerobic oxidative desulfurization of dibenzothiophenes. Green Chemistry, 18(2), 508-515. doi:10.1039/c5gc00862

Heterogeneous Pd-Catalyzed Efficient Synthesis of Imidazolones via Dehydrogenative Condensation between Ureas and 1,2-Diols

[EN] A heterogeneously catalyzed protocol for the acceptorless dehydrogenative condensation between N,N'-disubstituted ureas and 1,2-diols to afford imidazolones was developed. Palladium nanoaggregates stabilized onto an alumina matrix with suitable acidic properties, namely, [Pd/Al2O3], was designed and successfully applied as efficient and reusable heterogeneous nanocatalyst for this relevant transformation. The methodology developed showed its wide applicability through the synthesis of more than 25 imidazolones with moderate to good yields, reaching a turnover number (TON) of up to 19444 and a initial turnover frequency (TOF0) > 290 h(-1). The active nanostructured catalyst was fully characterized [X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), high-resolution scanning transmission electron microscopy (HR-STEM), energy-dispersive X-ray (EDX), Raman spectroscopy, temperature-programmed reduction (TPR), temperature-programmed desorption (TPD)-NH3, TPD-CO2, X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) area], and mechanistic studies were performed. Moreover, other related Pd-based nanomaterials composed of different acidic or basic inorganic supports were synthesized and extensively compared in this reaction. These studies revealed that the presence of Pd nanoparticles with a wide range of sizes (average particle size 2.8 nm) over a metal oxide support with a high density of acid sites is a key point for the good activity of the material, gamma-Al2O3 being the optimum support. Furthermore, a Pd-Zn cooperation effect was described for the dehydrogenative condensation of unactivated 1,2-diols, including ethylene glycol, with ureas. Two Pd-Zn bimetallic materials ([Pd/ZnO] and [Pd(5%)-Zn(5%)/Al2O3) were also designed and characterized properly. These materials, as well as the [Pd/Al2O3] system in combination with catalytic amounts of ZnO, showed good activity and selectivity in the acceptorless dehydrogenative condensation between ureas and unactivated 1,2-diols. The heterogeneous nature of all of the described catalytic systems was demonstrated, and the reusability of the catalysts was proven.This work was supported by the SEJI program funded by Generalitat Valenciana (Subvencions Excelencia Juniors Investigadors, grants SEJI/2019/006 and SEJI/2020/013), RETOS I+D+I program from MICINN (PID2019-109656RA-I0/AEI/10.13039/501100011033), and a program from "La Caixa" Foundation (ID 100010434), fellowship code LCF/BQ/PI18/11630023. J.R.C.-A. and R.A. are grateful to MICINN (Spanish Government) for two Ramon y Cajal contracts (ref RYC-2017-22717 and RYC2020-029493-I). The authors thank Dr. Maria Cabrero-Antonino for the fruitful discussions.Arango-Daza, JC.; Lluna-Galán, C.; Izquierdo-Aranda, L.; Cabrero Antonino, JR.; Adam, R. (2022). Heterogeneous Pd-Catalyzed Efficient Synthesis of Imidazolones via Dehydrogenative Condensation between Ureas and 1,2-Diols. ACS Catalysis. 12(12):6906-6922. https://doi.org/10.1021/acscatal.2c0142369066922121

Iron(III) Triflimide as a catalytic substitute for gold(I) in hydroaddition reactions to unsaturated carbon-carbon bonds

[EN] In this work it is shown that iron(III) and gold(I) triflimide efficiently catalyze the hydroaddition of a wide array of nucleophiles including water, alcohols, thiols, amines, alkynes, and alkenes to multiple CC bonds. The study of the catalytic activity and selectivity of iron(III), gold(I), and BrOnsted triflimides has unveiled that iron(III) triflimide [Fe(NTf2)3] is a robust catalyst under heating conditions, whereas gold(I) triflimide, even stabilized by PPh3, readily decomposes at 80 degrees C and releases triflimidic acid (HNTf2) that can catalyze the corresponding reaction, as shown by in situ 19F, 15N, and 31PNMR spectroscopy. The results presented here demonstrate that each of the two catalyst types has weaknesses and strengths and complement each other. Iron(III) triflimide can act as a substitute of gold(I) triflimide as a catalyst for hydroaddition reactions to unsaturated carbon-carbon bonds.The work has been supported by Consolider-Ingenio 2010 (proyecto MULTICAT). J.R.C.A. thanks MCIINN for the concession of a pre-doctoral FPU fellowship. A. L. P. thanks ITQ for financial support.Cabrero Antonino, JR.; Leyva Perez, A.; Corma Canós, A. (2013). Iron(III) Triflimide as a catalytic substitute for gold(I) in hydroaddition reactions to unsaturated carbon-carbon bonds. Chemistry - A European Journal. 19(26):8627-8633. https://doi.org/10.1002/chem.201300386S862786331926Brenzovich, W. E. (2012). Gold in der Totalsynthese: Alkine als Carbonylersatz. Angewandte Chemie, 124(36), 9063-9065. doi:10.1002/ange.201204598Brenzovich, W. E. (2012). Gold in Total Synthesis: Alkynes as Carbonyl Surrogates. Angewandte Chemie International Edition, 51(36), 8933-8935. doi:10.1002/anie.201204598Oliver-Meseguer, J., Cabrero-Antonino, J. R., Dominguez, I., Leyva-Perez, A., & Corma, A. (2012). Small Gold Clusters Formed in Solution Give Reaction Turnover Numbers of 107 at Room Temperature. Science, 338(6113), 1452-1455. doi:10.1126/science.1227813Corma, A., Leyva-Pérez, A., & Sabater, M. J. (2011). Gold-Catalyzed Carbon−Heteroatom Bond-Forming Reactions. Chemical Reviews, 111(3), 1657-1712. doi:10.1021/cr100414uKrause, N., & Winter, C. (2011). Gold-Catalyzed Nucleophilic Cyclization of Functionalized Allenes: A Powerful Access to Carbo- and Heterocycles. Chemical Reviews, 111(3), 1994-2009. doi:10.1021/cr1004088Huang, H., Zhou, Y., & Liu, H. (2011). Recent advances in the gold-catalyzed additions to C–C multiple bonds. Beilstein Journal of Organic Chemistry, 7, 897-936. doi:10.3762/bjoc.7.103Hashmi, A. S. K. (2010). Homogene Gold-Katalyse jenseits von Vermutungen und Annahmen - charakterisierte Intermediate. Angewandte Chemie, 122(31), 5360-5369. doi:10.1002/ange.200907078Hashmi, A. S. K. (2010). 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Nitro functionalized chromium terephthalate metal-organic framework as multifunctional solid acid for the synthesis of benzimidazoles

[EN] In the present work, nitro functionalized chromium terephthalate [MIL-101(Cr)-NO2] metal-organic framework is prepared and characterized by powder X-ray diffraction (XRD), elemental analysis, infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and Brun auer-Emmett-Teller (BET) surface area. The inherent Lewis acidity of MIL-101(Cr)-NO2 is confirmed by FT-IR spectroscopy using CD3CN as a probe molecule. The performance of MIL-101(Cr)-NO2 as bifunctional catalyst (acid and redox) promoting the synthesis of wide range of benzimidazoles has been examined by catalyzed condensation on acid sites and subsequent oxidative dehydrogenation. The catalytic activity of MIL-101(Cr)-NO2 is found to be superior than analogues catalysts like MIL-101(Cr)-S0(3)H, MIL-101(Cr)-NH2, U10-66(Zr), Ui0-66(Zr)-NO2, MIL-100(Fe) and Cu-3(BTC)(2) (BTC: 1,35-benzenetricarboxylate) under identical reaction conditions, The structural stability of MIL-101(Cr)-NO2 is supported by leaching analysis and reusability tests. MIL-101(Cr)-NO2 solid is used five times without decay in its activity. Comparison of the fresh and five times used MIL-101(Cr)-NO2 solids by powder XRD, SEM and elemental analysis indicate identical crystallinity, morphology and the absence of chromium leaching, respectively. (C) 2019 Elsevier Inc. All rights reserved.AD thanks the University Grants Commission, New Delhi, for the award of an Assistant Professorship under its Faculty Recharge Programme. AD also thanks the Department of Science and Technology, India, for the financial support through Extra Mural Research Funding (EMR/2016/006500). Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-098237-CO21) and Generalitat Valenciana (Prometeo 2017/083) is gratefully acknowledged. S.N. thanks financial support by the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudication de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016), Ministerio de Ciencia, Innovation y Universidades RTI2018-099482-A-I00 project and Generalitat Valenciana grupos de investigacion consolidables 2019 (AICO/2019/214) project.Vallés-García, C.; Cabrero-Antonino, M.; Navalón Oltra, S.; Alvaro Rodríguez, MM.; Dhakshinamoorthy, A.; García Gómez, H. (2020). Nitro functionalized chromium terephthalate metal-organic framework as multifunctional solid acid for the synthesis of benzimidazoles. 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