The Pivotal Role of Catalysis in France: Selected Examples of Recent Advances and Future Prospects.

Olivier‐Bourbigou, Hélène; Chizallet, Céline; Dumeignil, Franck; Fongarland, Pascal; Geantet, Christophe; Granger, Pascal; Launay, Franck; Löfberg, Axel; Massiani, Pascale; Maugé, Françoise; Ouali, Armelle; Roger, Anne‐Cécile; Schuurman, Y.; Tanchoux, Nathalie; Uzio, Denis; Jérôme, François; Duprez, Daniel; Pinel, Catherine

doi:10.1002/cctc.201700426

Cited by 4 publications

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References 566 publications

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“…Studies involving second generation biomass, especially lignocellulose (wood and grassy plants), have started more recently and are now predominant. All the past and current research in this area has given to our team a certain notoriety within the French catalysis and green chemistry communities [35]. We would like to present here an overview of the research performed in the C'Durable team on the transformation of lignocellulosic biopolymers.…”

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A Landscape of Lignocellulosic Biopolymer Transformations into Valuable Molecules by Heterogeneous Catalysis in C’Durable Team at IRCELYON

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This review article highlights part of the research activity of the C’Durable team at IRCELYON in the field of sustainable chemistry. This review presents a landscape of the work performed on the valorization of lignocellulosic biopolymers. These studies intend to transform cellulose, hemicellulose and lignin into valuable molecules. The methodology usually consists in evaluating the behavior of the biopolymers in the absence of catalyst under various conditions (solvent, temperature), and then to assess the influence of a catalyst, most often a heterogeneous catalyst, on the reactivity. The most significant results obtained on the upgrading of cellulose and lignin, which have been mainly investigated in the team, will be presented with an opening on studies involving raw lignocellulose.

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Section: Introductionmentioning

confidence: 99%

A Landscape of Lignocellulosic Biopolymer Transformations into Valuable Molecules by Heterogeneous Catalysis in C’Durable Team at IRCELYON

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“…In the last years, DivCat worked on bringing researchers from different subfields of catalysis together to spread recent results efficiently and to promote the emergence of new ideas. DivCat is also at the origin of the Review published in the present special issue, “The pivotal role of catalysis in France: selective examples of recent advances and future prospects” …”

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The French Conference on Catalysis—FCCat 1

et al. 2017

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CatalysisinFrance is an adventure with al ong traditioni llustrated with major discoveriesa nd famous scientists. More than 100 years ago, Paul Sabatier (Nobel Laureate in 1912) and JeanBaptiste Senderens discovered the activity of finely divided metals in hydrogenation of olefins and other unsaturated compounds;t hese results laid the groundworkf or today's industrial catalysis. In the 1920's, the French Engineer Eugene Houdrys tartedh is research on the production of gasoline from lignite in France, then he movedt oU nited States and openedt he way to the catalytic conversion of crude petroleumt oh igh-octane gasoline. Boris Imelik was ap ioneer in the use of physico-chemical techniquesf or catalystc haracterization. FranÅois Gault, ab rilliant French scientist, workedo n catalytic mechanisms. We pay tribute to his memory by awarding the Francois GaultL ectureship, the highest European distinctioni nt he field of catalysis (EFCATS lecture series). Prettre, Germain, Teichner,M aurel, Barthomeuf, amongo thers, fascinated by catalysis, played am ajor role in the development of catalysis at nationala nd international levels.T his tradition continued with Yves Chauvin's innovations, Nobel Laureate in 2005, who discovered the metathesis mechanism and Henri Kagan's pioneer work in asymmetricc atalysis. France contributed to the promotion and the development of the global catalysis community by organizing in Paris two editions of the International Congress on Catalysis:t he 2 nd ICC (1960) and 13 th ICC (2004) and two editionso fE uropacat:t he first (1993-Montpellier) and the 13 th (2013-Lyon) editions. Today,t he younger generation of French researchers and engineers in catalysis work in more than 30 academic laboratories and research institutes. They are sharing the same enthusiasm and flame and have understood the role that catalysis hast op lay to face the main challenges of our society.Beyond the individual success stories,t he FrenchC atalysis community has ap articular history comingf rom conflicts and convergences between its researchers and schools. The French Catalysis developeda sadistinct scientific field in the 1960's with the support of CNRS, universities,a nd the coal and oil industry.A tt he end of the 1960's, several of the French industrial and academic labs were strengthening their expertise in specificf ields (catalysts cience, catalytic reactions and mechanisms, and appliedc atalysis), but they were missing at ool to share the knowledge as awhole community.

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“…128 Drug discovery, alternative energy, and materials synthesis are the few subjects enabled by this field of study. [129][130] Transition metal complexes are the most successful and well-known catalysts for practical TH of ketones due to their high catalytic activity, selectivity and stability. TMCs have predominated the field of TH of ketones for decades.…”

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Carboxamide ruthenium(II) and manganese(II) complexes: structural, kinetic, and mechanistic studies in the transfer hydrogenation of ketones.

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The carboxamide ligands N-(benzo[d]thiazol-2-yl)pyrazine-2-carboxamide (HL1), N-(1H-benzo[d]imidazol-2-yl)pyrazine-2-carboxamide (HL2), were prepared by condensation of pyrazine-carboxylic acid and appropriate heteroaromatic amines. Reactions of HL1 and HL2 with ruthenium(II) precursors, [RuH(CO)Cl(PPh3)3] and [RuH2(CO)(PPh3)3] afforded the mononuclear complexes [RuL1(PPh3)2(CO)Cl] (Ru1), [RuL1(PPh3)2(CO)H] (Ru2), [RuL2(PPh3)2(CO)Cl] (Ru3), [RuL2(PPh3)2(CO)H] (Ru4). The solid-state structures of complexes Ru1, Ru2, and Ru4 reveal bidentate modes of coordination of the ligands and distorted octahedral geometries around the Ru(II) centre. The complexes formed active catalysts in the transfer hydrogenation of ketones and achieved turnover number (TON) up to 530 in 6 h. The ruthenium(II)–hydride complexes, Ru2 and Ru4, were capable of catalysing transfer hydrogenation of ketones reactions under base free reaction conditions and demonstrated higher catalytic activities compared to the corresponding non-hydride analogues (Ru1 and Ru3). An inner sphere monohydride mechanism involving dissociation of one PPh3 group was proposed from in situ 31P{1H} NMR spectroscopy studies. Dipicolinamide ligand system, N,N'-(1,4 phenylene)dipicolinamide (H2L3), N,N'-(1,2-phenylene)dipicolinamide (H2L4), N,N'-(4,5-dimethyl-1,2-phenylene)dipicolinamide (H2L5), N,N'-(4-methoxy-1,2-phenylene)dipicolinamide (H2L6) were synthesised following a similar protocol described for HL1 and HL2. Treatment of the ligands H2L3 and H2L4 with RuH(CO)Cl(PPh3)3 afforded bimetallic complexes [Ru2(H2L3)(PPh3)4(CO)2][2Cl] (Ru5), [Ru2(H2L3)(H)2(PPh3)4(CO)2] (Ru5b), [Ru2(HL4)(PPh3)3(CO)2Cl3] (Ru6) and a mononuclear complex [RuCl2L4(PPh3)2(CO)] (Ru7). The solid-sate structure of the dinuclear ruthenium(II) complexes confirmed a bidentate coordinate mode, with PPh3, CO, and chlorido auxiliary ligands occupying the remaining coordinating sites to afford distorted trigonal bipyramidal geometries (Ru5 and Ru6) while the mononuclear complex Ru7 adopted a distorted octahedral geometry around its ruthenium(II) atom. The reaction of the ligands H2L4-H2L6 with the [RuCl2-η6-p-cymene]2 precursor produces half-sandwich diruthenium complexes [{Ru(η6-p-cymene)}2-μ-Cl(L4)][Ru(η6-p-cymene)Cl3] (Ru8), [{Ru(η6-p-cymene)}2-μ-Cl(L4)][PF6] (Ru9), [{Ru(η6-p-cymene)}2-μ-Cl(L5)][PF6] (Ru10), and [{Ru(η6-p-cymene)}2-μ-Cl (L6)][PF6] (Ru11). The molecular structure of cationic complexes, Ru8-Ru11, was confirmed by single-crystal X-ray crystallography analysis. The complexes Ru8-Ru11 display a bidentate Npyridine ^ Namidate mode of coordination to give pseudo-octahedral geometry (piano-stool-like geometry). The ruthenium(II) complexes demonstrated remarkable enhanced catalytic activity (TON values up to 1.71 x 104) in the transfer hydrogenation of ketones at a very low catalyst loading of 2.75 x10-2 mol% (275 ppm). The dinuclear ruthenium(II) complexes showed higher catalytic activity compared to the corresponding mononuclear complex Ru5. The half-sandwich diruthenium complexes Ru8-Ru11 displayed relatively higher catalytic activity than the ruthenium complexes Ru5 and Ru6 bearing the PPh3 co-ligands. Monohydride inner-sphere catalytic cycle was proposed for the transfer hydrogenation of ketones catalysed by both Ru1 and Ru9, and the formation of the reactive intermediates was supported with low-resolution mass spectrometry data. The dinuclear ruthenium complexes of pyridine and pyrazine-carboxamide bearing quinolinyl motif were synthesised by reacting, N-(quinolin-8-yl)pyrazine-2-carboxamide, (HL7), 5-methyl-N-(quinolin-8-yl)pyridine-2-carboxamide, (HL8), 5-chloro-N-(quinolin-8-yl)pyridine-2-carboxamide, (HL9), and 2-pyrazine-carboxylic acid (HL10) with equimolar [RuCl2(η6-p-cymene)]2 to afford the dinuclear complexes [{Ru(η6-p-cymene)}2Cl3(L10)] (Ru12), [{Ru(η6-p-cymene)Cl}2(L7)] [PF6] (Ru13), [{Ru(η6-p-cymene)Cl}2(L8)][Ru(L8)Cl3] (Ru14), and [{Ru(η6-p-cymene)Cl}2(L9)][PF6] (Ru15), respectively. The solid-state structures of the dinuclear complexes Ru12 and Ru13 reveal a typical piano-stool geometry around the Ru(II) ions. The dinuclear ruthenium complexes Ru12-Ru15 were used as catalysts in the transfer hydrogenation of a broad spectrum of aldehydes and ketones and demonstrated excellent catalytic activity, TON values up to 4.8 x 104, using catalyst loading of 2.0 x10-3 mol% (20 ppm). The catalytic performance of the complexes was affected by the ligand architecture and the substituents on the pyridyl ring. Complexes Ru13-15 exhibited higher catalytic activities compared to the complex Ru12 which could be ascribed to the role of quinoline in stabilising the complexes. The pyridine and pyrazine motifs have a significant impact on the reactivity and the catalytic activity of the complexes. In-situ low-resolution ESI-MS analyses of the reactive intermediates aided in proposing a monohydride inner-sphere mechanism for the transfer hydrogenation of ketones catalysed by Ru15. To develop a more sustainable, environmentally compatible and cost-efficient protocol for transfer hydrogenation of ketones, a new catalytic system based on manganese(II) metal was synthesised. New manganese(II) complexes Mn1-Mn4, ligated on dipicolinamide ligands were synthesized by treating the N,N'-(1,4-phenylene)dipicolinamide (H2L3), N,N'-(1,2-phenylene)dipicolinamide (H2L4), N,N'-(4-methoxy-1,2-phenylene)dipicolinamide (H2L5) and N,N'-(4,5-dimethyl-1,2-phenylene)dipicolinamide (H2L6) with MnCl2.4H2O salt to afford dinuclear manganese(II) complexes [Mn2(H2L3)2Cl4] (Mn1), [Mn2(H2L4)2Cl4] (Mn2), [Mn2(H2L5)2(Cl)4] (Mn3) and [Mn2(H2L6)2Cl4] (Mn4). The solid-state structure of complex Mn2 showed a six-coordinate dinuclear complex with the two Mn(II) ions adopting a distorted octahedral environment surrounded by two tetradentate ligands and chlorido co-ligands, respectively. The Mn(II) complexes formed active catalysts in transfer hydrogenation of ketones to achieve TON values up to 5.12 x 104. The presence of electron-donating substituents -OCH3 and -CH3 in complexes Mn3 and Mn4 displayed minor effects in the transfer hydrogenation of ketones. The new carboxamide-manganese(II) complexes are among the most active manganese-based catalysts capable of hydrogenating a large scope of ketones ranging from aliphatic to aromatic ketones. A dihydride catalytic cycle has been proposed and supported with in-situ low-resolution mass spectrometry data.

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The Pivotal Role of Catalysis in France: Selected Examples of Recent Advances and Future Prospects.

Abstract: International audienc

Cited by 4 publications

References 566 publications

A Landscape of Lignocellulosic Biopolymer Transformations into Valuable Molecules by Heterogeneous Catalysis in C’Durable Team at IRCELYON

A Landscape of Lignocellulosic Biopolymer Transformations into Valuable Molecules by Heterogeneous Catalysis in C’Durable Team at IRCELYON

The French Conference on Catalysis—FCCat 1

Carboxamide ruthenium(II) and manganese(II) complexes: structural, kinetic, and mechanistic studies in the transfer hydrogenation of ketones.

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