Metal-Free Dehydrogenation of Formic Acid to H2 and CO2 Using Boron-Based Catalysts

International audienceFormic acid is at the crossroads of novel sustainable energy strategies because it is an efficient H2 carrier. Yet, its decomposition to H2 today relies on metal-based catalysts. Herein, we describe the first metal-free catalysts able to promote the dehydrogenation of formic acid. Using dialkylborane derivatives, HCOOH is decomposed to H2 and CO2, in the presence of a base, with high selectivity. Experimental and computational results point to the involvement of bis(formyloxy)borates as key intermediates in the C–H bond activation of a formate ligan

A pre-clinical validation plan to evaluate analytical sensitivities of molecular diagnostics such as BD MAX MDR-TB, Xpert MTB/Rif Ultra and FluoroType MTB

Rapid diagnosis of tuberculosis (TB) and antibiotic resistances are imperative to initiate effective treatment and to stop transmission of the disease. A new generation of more sensitive, automated molecular TB diagnostic tests has been recently launched giving microbiologists more choice between several assays with the potential to detect resistance markers for rifampicin and isoniazid. In this study, we determined analytical sensitivities as 95% limits of detection (LoD(95)) for Xpert MTB/Rif Ultra (XP-Ultra) and BD-MAX MDR-TB (BD-MAX) as two representatives of the new test generation, in comparison to the conventional FluoroType MTB (FT-MTB). Test matrices used were physiological saline solution, human and a mucin-based artificial sputum (MUCAS) each spiked with Mycobacterium tuberculosis in declining culture- and qPCR-controlled concentrations. With BD-MAX, XP-Ultra, and FTMTB, we measured LoD(95)(TB) values of 2.1 cfu/ml (CI95%: 0.9-23.3), 3.1 cfu/ml (CI95%: 1.288.9), and 52.1 cfu/ml (CI95%: 16.7-664.4) in human sputum;of 6.3 cfu/ml (CI95%: 2.931.8), 1.5 cfu/ml (CI95%: 0.7-5.0), and 30.4 cfu/ml (CI95%: 17.4-60.7) in MUCAS;and of 2.3 cfu/ml (CI95%: 1.1-12.0), 11.5 cfu/ml (CI95%: 5.6-47.3), and 129.1 cfu/ml (CI95%: 82.8-273.8) in saline solution, respectively. LoD(95) of resistance markers were 9 to 48 times higher compared to LoD(95)(TB). BD-MAX and XP-Ultra have an equal and significantly increased analytical sensitivity compared to conventional tests. MUCAS resembled human sputum, while both yielded significantly different results than normal saline. MUCAS proved to be suitable for quality control of PCR assays for TB diagnostics

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). Homogeneous Gold Catalysis Beyond Assumptions and Proposals-Characterized Intermediates. Angewandte Chemie International Edition, 49(31), 5232-5241. doi:10.1002/anie.200907078Beaumont, S. K., Kyriakou, G., & Lambert, R. M. (2010). Identity of the Active Site in Gold Nanoparticle-Catalyzed Sonogashira Coupling of Phenylacetylene and Iodobenzene. Journal of the American Chemical Society, 132(35), 12246-12248. doi:10.1021/ja1063179Marion, N., Ramón, R. S., & Nolan, S. P. (2009). [(NHC)AuI]-Catalyzed Acid-Free Alkyne Hydration at Part-per-Million Catalyst Loadings. Journal of the American Chemical Society, 131(2), 448-449. doi:10.1021/ja809403eGrirrane, A., Corma, A., & Garcia, H. (2008). Gold-Catalyzed Synthesis of Aromatic Azo Compounds from Anilines and Nitroaromatics. Science, 322(5908), 1661-1664. doi:10.1126/science.1166401Corma, A., & Garcia, H. (2008). Supported gold nanoparticles as catalysts for organic reactions. Chemical Society Reviews, 37(9), 2096. doi:10.1039/b707314nGonzález-Arellano, C., Abad, A., Corma, A., García, H., Iglesias, M., & Sánchez, F. (2007). Catalysis by Gold(I) and Gold(III): A Parallelism between Homo- and Heterogeneous Catalysts for Copper-Free Sonogashira Cross-Coupling Reactions. Angewandte Chemie, 119(9), 1558-1560. doi:10.1002/ange.200604746González-Arellano, C., Abad, A., Corma, A., García, H., Iglesias, M., & Sánchez, F. (2007). Catalysis by Gold(I) and Gold(III): A Parallelism between Homo- and Heterogeneous Catalysts for Copper-Free Sonogashira Cross-Coupling Reactions. Angewandte Chemie International Edition, 46(9), 1536-1538. doi:10.1002/anie.200604746Hashmi, A. S. K. (2007). Gold-Catalyzed Organic Reactions. Chemical Reviews, 107(7), 3180-3211. doi:10.1021/cr000436xWienhöfer, G., Westerhaus, F. A., Jagadeesh, R. V., Junge, K., Junge, H., & Beller, M. (2012). Selective iron-catalyzed transfer hydrogenation of terminal alkynes. Chemical Communications, 48(40), 4827. doi:10.1039/c2cc31091kCabrero-Antonino, J. R., Leyva-Pérez, A., & Corma, A. (2012). Iron-Catalysed Markovnikov Hydrothiolation of Styrenes. Advanced Synthesis & Catalysis, 354(4), 678-687. doi:10.1002/adsc.201100731Cabrero-Antonino, J. R., Leyva-Pérez, A., & Corma, A. (2012). Regioselective Hydration of Alkynes by Iron(III) Lewis/Brønsted Catalysis. Chemistry - A European Journal, 18(35), 11107-11114. doi:10.1002/chem.201200580Boddien, A., Mellmann, D., Gartner, F., Jackstell, R., Junge, H., Dyson, P. J., … Beller, M. (2011). Efficient Dehydrogenation of Formic Acid Using an Iron Catalyst. Science, 333(6050), 1733-1736. doi:10.1126/science.1206613Sun, C.-L., Li, B.-J., & Shi, Z.-J. (2011). Direct C−H Transformation via Iron Catalysis. Chemical Reviews, 111(3), 1293-1314. doi:10.1021/cr100198wJunge, K., Schröder, K., & Beller, M. (2011). Homogeneous catalysis using iron complexes: recent developments in selective reductions. Chemical Communications, 47(17), 4849. doi:10.1039/c0cc05733aZhou, S., Fleischer, S., Junge, K., Das, S., Addis, D., & Beller, M. (2010). Asymmetrische Synthese von Aminen: eine allgemeine und effiziente eisenkatalysierte enantioselektive Transferhydrierung von Iminen. Angewandte Chemie, 122(44), 8298-8302. doi:10.1002/ange.201002456Zhou, S., Fleischer, S., Junge, K., Das, S., Addis, D., & Beller, M. (2010). Enantioselective Synthesis of Amines: General, Efficient Iron-Catalyzed Asymmetric Transfer Hydrogenation of Imines. Angewandte Chemie International Edition, 49(44), 8121-8125. doi:10.1002/anie.201002456Cabrero-Antonino, J. R., Leyva-Pérez, A., & Corma, A. (2010). Iron-Catalysed Regio- and Stereoselective Head-to-Tail Dimerisation of Styrenes. Advanced Synthesis & Catalysis, 352(10), 1571-1576. doi:10.1002/adsc.201000096Zhou, S., Junge, K., Addis, D., Das, S., & Beller, M. (2009). A Convenient and General Iron-Catalyzed Reduction of Amides to Amines. Angewandte Chemie, 121(50), 9671-9674. doi:10.1002/ange.200904677Zhou, S., Junge, K., Addis, D., Das, S., & Beller, M. (2009). A Convenient and General Iron-Catalyzed Reduction of Amides to Amines. Angewandte Chemie International Edition, 48(50), 9507-9510. doi:10.1002/anie.200904677Kohno, K., Nakagawa, K., Yahagi, T., Choi, J.-C., Yasuda, H., & Sakakura, T. (2009). Fe(OTf)3-Catalyzed Addition of sp C−H Bonds to Olefins. Journal of the American Chemical Society, 131(8), 2784-2785. doi:10.1021/ja8090593Correa, A., García Mancheño, O., & Bolm, C. (2008). Iron-catalysed carbon–heteroatom and heteroatom–heteroatom bond forming processes. Chemical Society Reviews, 37(6), 1108. doi:10.1039/b801794hMichaux, J., Terrasson, V., Marque, S., Wehbe, J., Prim, D., & Campagne, J.-M. (2007). Intermolecular FeCl3-Catalyzed Hydroamination of Styrenes. European Journal of Organic Chemistry, 2007(16), 2601-2603. doi:10.1002/ejoc.200700023Bolm, C., Legros, J., Le Paih, J., & Zani, L. (2004). Iron-Catalyzed Reactions in Organic Synthesis. Chemical Reviews, 104(12), 6217-6254. doi:10.1021/cr040664hFürstner, A., Leitner, A., Méndez, M., & Krause, H. (2002). Iron-Catalyzed Cross-Coupling Reactions. Journal of the American Chemical Society, 124(46), 13856-13863. doi:10.1021/ja027190tKischel, J., Jovel, I., Mertins, K., Zapf, A., & Beller, M. (2006). A Convenient FeCl3-Catalyzed Hydroarylation of Styrenes. Organic Letters, 8(1), 19-22. doi:10.1021/ol0523143Patil, N. T., Kavthe, R. D., & Shinde, V. S. (2012). Transition metal-catalyzed addition of C-, N- and O-nucleophiles to unactivated C–C multiple bonds. Tetrahedron, 68(39), 8079-8146. doi:10.1016/j.tet.2012.05.125Beller, 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.200300616Beller, 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.200300616Hashmi, A. S. K. (2007). Homogeneous gold catalysis: The role of protons. Catalysis Today, 122(3-4), 211-214. doi:10.1016/j.cattod.2006.10.006Hashmi, A. S. K., Schwarz, L., Rubenbauer, P., & Blanco, M. C. (2006). The Condensation of Carbonyl Compounds with Electron-Rich Arenes: Mercury, Thallium, Gold or a Proton? Advanced Synthesis & Catalysis, 348(6), 705-708. doi:10.1002/adsc.200505464Williamson, K. S., & Yoon, T. P. (2012). Iron Catalyzed Asymmetric Oxyamination of Olefins. Journal of the American Chemical Society, 134(30), 12370-12373. doi:10.1021/ja3046684Hashmi, A. S. K., Braun, I., Nösel, P., Schädlich, J., Wieteck, M., Rudolph, M., & Rominger, F. (2012). Eine einfache Gold-katalysierte Synthese von Benzofulvenen -gem-diaurierte Spezies als «Instant-Dual-Activation»-Präkatalysatoren. Angewandte Chemie, 124(18), 4532-4536. doi:10.1002/ange.201109183Hashmi, A. S. K., Braun, I., Nösel, P., Schädlich, J., Wieteck, M., Rudolph, M., & Rominger, F. (2012). Simple Gold-Catalyzed Synthesis of Benzofulvenes-gem-Diaurated Species as «Instant Dual-Activation» Precatalysts. Angewandte Chemie International Edition, 51(18), 4456-4460. doi:10.1002/anie.201109183Antoniotti, S., Dalla, V., & Duñach, E. (2010). Metalltriflimidate sind bessere Katalysatoren für die organische Synthese als Metalltriflate - der Effekt eines stark delokalisierten Gegenions. Angewandte Chemie, 122(43), 8032-8060. doi:10.1002/ange.200906407Antoniotti, S., Dalla, V., & Duñach, E. (2010). Metal Triflimidates: Better than Metal Triflates as Catalysts in Organic Synthesis-The Effect of a Highly Delocalized Counteranion. Angewandte Chemie International Edition, 49(43), 7860-7888. doi:10.1002/anie.200906407Ricard, L., & Gagosz, F. (2007). Synthesis and Reactivity of Air-Stable N-Heterocyclic Carbene Gold(I) Bis(trifluoromethanesulfonyl)imidate Complexes. Organometallics, 26(19), 4704-4707. doi:10.1021/om7006002Dang, T. T., Boeck, F., & Hintermann, L. (2011). Hidden Brønsted Acid Catalysis: Pathways of Accidental or Deliberate Generation of Triflic Acid from Metal Triflates. The Journal of Organic Chemistry, 76(22), 9353-9361. doi:10.1021/jo201631xTaylor, J. G., Adrio, L. A., & Hii, K. K. (Mimi). (2010). Hydroamination reactions by metal triflates: Brønsted acid vs. metal catalysis? Dalton Trans., 39(5), 1171-1175. doi:10.1039/b918970jKovács, G., Lledós, A., & Ujaque, G. (2010). Mechanistic Comparison of Acid- and Gold(I)-Catalyzed Nucleophilic Addition Reactions to Olefins. Organometallics, 29(22), 5919-5926. doi:10.1021/om1007192Li, Z., Zhang, J., Brouwer, C., Yang, C.-G., Reich, N. W., & He, C. (2006). Brønsted Acid Catalyzed Addition of Phenols, Carboxylic Acids, and Tosylamides to Simple Olefins. Organic Letters, 8(19), 4175-4178. doi:10.1021/ol0610035(s. f.). doi:10.1021/ol061174Wabnitz, T. C., Yu, J.-Q., & Spencer, J. B. (2004). Evidence That Protons Can Be the Active Catalysts in Lewis Acid Mediated Hetero-Michael Addition Reactions. Chemistry - A European Journal, 10(2), 484-493. doi:10.1002/chem.200305407Penzien, J., Su, R. Q., & Müller, T. E. (2002). The role of protons in hydroamination reactions involving homogeneous and heterogeneous catalysts. Journal of Molecular Catalysis A: Chemical, 182-183, 489-498. doi:10.1016/s1381-1169(01)00496-4Weïwer, M., Coulombel, L., & Duñach, E. (2006). Regioselective indium(iii) trifluoromethanesulfonate-catalyzed hydrothiolation of non-activated olefins. Chem. Commun., (3), 332-334. doi:10.1039/b513946eLeyva, A., & Corma, A. (2009). Isolable Gold(I) Complexes Having One Low-Coordinating Ligand as Catalysts for the Selective Hydration of Substituted Alkynes at Room Temperature without Acidic Promoters. The Journal of Organic Chemistry, 74(5), 2067-2074. doi:10.1021/jo802558eLeyva, A., & Corma, A. (2009). Reusable Gold(I) Catalysts with Unique Regioselectivity for Intermolecular Hydroamination of Alkynes. Advanced Synthesis & Catalysis, 351(17), 2876-2886. doi:10.1002/adsc.200900491Arvai, R., Toulgoat, F., Langlois, B. R., Sanchez, J.-Y., & Médebielle, M. (2009). A simple access to metallic or onium bistrifluoromethanesulfonimide salts. Tetrahedron, 65(27), 5361-5368. doi:10.1016/j.tet.2009.04.068Hashmi, A. S. K., Blanco, M. C., Fischer, D., & Bats, J. W. (2006). Gold Catalysis: Evidence for the In-situ Reduction of Gold(III) During the Cyclization of Allenyl Carbinols. European Journal of Organic Chemistry, 2006(6), 1387-1389. doi:10.1002/ejoc.200600009Morita, N., & Krause, N. (2006). Erste goldkatalysierte C-S-Bindungsknüpfung: Cycloisomerisierung von α-Thioallenen zu 2,5-Dihydrothiophenen. Angewandte Chemie, 118(12), 1930-1933. doi:10.1002/ange.200503846Morita, N., & Krause, N. (2006). The First Gold-Catalyzed CS Bond Formation: Cycloisomerization of α-Thioallenes to 2,5-Dihydrothiophenes. Angewandte Chemie International Edition, 45(12), 1897-1899. doi:10.1002/anie.200503846Santos, L. L., Ruiz, V. R., Sabater, M. J., & Corma, A. (2008). Regioselective transformation of alkynes into cyclic acetals and thioacetals with a gold(I) catalyst: comparison with Brønsted acid catalysts. Tetrahedron, 64(34), 7902-7909. doi:10.1016/j.tet.2008.06.032Hashimoto, T., Kutubi, S., Izumi, T., Rahman, A., & Kitamura, T. (2011). Catalytic hydroarylation of alkynes with arenes in the presence of FeCl3 and AgOTf. Journal of Organometallic Chemistry, 696(1), 99-105. doi:10.1016/j.jorganchem.2010.08.009Corma, A., Ruiz, V. R., Leyva-Pérez, A., & Sabater, M. J. (2010). 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Towards sustainable production of formic acid

peer-reviewedFormic acid is a widely used commodity chemical. It can be applied as a safe, easily handled and transported source of hydrogen or CO for different reactions including those producing fuels. The review includes historical aspects of formic acid production. It shortly analyzes the production based on traditional sources such as toxic CO, methanol and methane. However, the main emphasis is done to the sustainable production of formic acid from biomass and biomass-derived products via hydrolysis, wet and catalytic oxidation processes. New strategies of low temperature synthesis from biomass may lead to utilization of formic acid for production of fuel additives such as methanol, upgraded bio-oil, γ-valerolactone and its derivatives, as well as synthesis gas used for Fischer-Tropsch synthesis of hydrocarbons. Some technological aspects are considered

Formic acid synthesis using CO₂ as raw material: Techno-economic and environmental evaluation and market potential

The future of carbon dioxide utilisation (CDU) processes, depend on (i) the future demand of synthesised products with CO₂, (ii) the availability of captured and anthropogenic CO₂, (iii) the overall CO₂ not emitted because of the use of the CDU process, and (iv) the economics of the plant. The current work analyses the mentioned statements through different technological, economic and environmental key performance indicators to produce formic acid from CO₂, along with their potential use and penetration in the European context. Formic acid is a well-known chemical that has potential as hydrogen carrier and as fuel for fuel cells. This work utilises process flow modelling, with simulations developed in CHEMCAD, to obtain the energy and mass balances, and the purchase equipment cost of the formic acid plant. Through a financial analysis, with the net present value as selected metric, the price of the tonne of formic acid and of CO₂ are varied to make the CDU project financially feasible. According to our research, the process saves CO₂ emissions when compared to its corresponding conventional process, under specific conditions. The success or effectiveness of the CDU process will also depend on other technologies and/or developments, like the availability of renewable electricity and steam