Catalysis and sustainable chemistry

One of the objectives of the development of new platforms based on POMs is to adapt the properties of the polyoxometallic backbone in order to meet the contemporary challenges of sustainable chemistry. The main applications of POMs in catalysis are based on their acid and/or redox properties, but also on their thermal stability and stability under oxidizing conditions, which make them efficient and recyclable (photo)catalysts, models of supported oxides for oxidation reactions (dehydrogenation, epoxidation, oxidative carboxylation…) meeting the criteria of efficiency and recyclability with a low environmental impact (G. Guillemot, R. Villanneau) We are also developing the synthesis of hybrid polyoxometallates and Schiff base complexes (salen) able to graft into mesoporous materials for the transformation of biomass substrates, in particular via CO2 activation (R. Villanneau).
The ability of polyanions to store several electrons, and, once reduced, several protons, can also be exploited in organic-inorganic hybrids by grafting, on the surface of the polyanion, model bio-inspired complexes of metalloenzyme active site. The POM is then used to reproduce the role of second-sphere interactions, in synergy with the catalyst (S. Blanchard).

Keywords: POM-based catalysts for sustainable chemistry, non-innocent ligands, supported homogeneous catalysis, second sphere interactions.

Unveiling the Active Surface Sites in Heterogeneous Titanium–Based Silicalite Epoxidation Catalysts : the Input of Silanol–Functionalized Polyoxotungstates as Soluble Analogues

T. Zhang, L. Mazaud, L.-M. Chamoreau, C. Paris, A. Proust and G. Guillemot ACS Catal. 2018, 8, 2330-2342.

In this contribution we discussed the preparation and characterization of titanium derivatives that proved relevant structural models for single-site silica-supported titanium catalysts, especially the defective open-lattice sites that are present in the MFI framework of the titanium-silicalite TS–1. The combined use of UV-Vis, Raman and NMR spectroscopies with Reaction Progress Kinetic Analysis methodologies permitted (i) to map a reliable picture of the catalytic mechanism over the course of the oxidation of allylic alcohols with aqueous hydrogen peroxide, and (ii) to indicate that Ti-hydroperoxyde Ti–(OOH) is the active species responsible for a high selectivity towards epoxide. To the best of our knowledge, [SbW9O33(tBuSiO)3Ti(OiPr)]3- represents the first example of a soluble titanium complex (i) that structurally models the open sites of TS-1, (ii) that is able to carry out the epoxidation of olefin with H2O2 without the need of embedment into a hydrophobic environment such as polymers, (iii) for which a complete understanding of the active intermediates and catalytic mechanism has been clearly established.

Oxidovanadium(V) Anchored to Silanol-​Functionalized Polyoxotungstates : Molecular Models for Single-​Site Silica-​Supported Vanadium Catalysts

G. Guillemot, E. Matricardi, L.-M. Chamoreau, R. Thouvenot, A. Proust, ACS Catalysis, 2015, 5(12), 7415-7423.

The metalation of two different types of silanol-​decorated polyoxotungstates, [XW9O34-​x(tBuSiOH)​3]​3-​ (X = P, x = 0 ; X = Sb, x = 1) and [PW10O36(tBuSiOH)​2]​3-​, by Cl3VO or (iPrO)​3 VO was achieved. The characterization of the resulting oxidovanadium(V)complexes [XW9O34-​x(tBuSiO)​3VO]​3-​ (X = P, 3 ; X = Sb, 3’) and [PW10O36(tBuSiO)​2VO(iPrO)​]​3-​ (4) was fully detailed, including x-​ray anal. These compds. are present in monomeric forms and therefore represent original mol. models for tris-​grafted and bis-​grafted isolated (V=O)​3+ species dispersed onto SiO2. Their ability as precatalysts for the epoxidn. of cyclic olefins and allylic alcs. with tert-​Bu hydroperoxide (TBHP) was studied. Probably a confined tris-​grafted species, such as 3 or 3’, does not act as an efficient catalyst whereas a more labile bis-​grafted species, such as 4, does. To gain a better understanding, the authors have assessed their suitability for ligand exchange with alcs. and TBHP and performed reaction progress kinetic anal. by monitoring the epoxidn. of 3-​methyl-​2-​buten-​1-​ol by 1H and 51V NMR.

Design of simple salophen chromium complexes for a two-steps oxidative carboxylation of styrene with CO2 and O2

M. Balas, R. Villanneau, F. Launay, J. CO2 Util. 72, 2023, 102497

Chromium(III) Salophen complexes bearing tertiary dialkyl amino substituents were synthesized and tested as homogeneous co-catalysts associated with n-Bu4NBr for the two-steps oxidative carboxylation on styrene using a mixture of O2 and CO2. The direct conversion (overall yield = 31%) of styrene into styrene carbonate was conducted at 80 °C with O2 and CO2 with a delayed addition of the cycloaddition catalysts (n-Bu4NBr and Salophen-Me2N-Cr) and CO2(11 bar). This work demonstrates that the key-point to afford a high styrene carbonate global yield with that system was related to the implementation of a two-step protocol, since it allowed to minimize the amounts of undesired by-products

Electro-​Assisted Reduction of CO2 to CO and Formaldehyde by (TOA)​6[α-​SiW11O39Co(_)​] Polyoxometalate

M. Girardi, S. Blanchard, S. Griveau, P. Simon, M. Fontecave, F. Bedioui, A. Proust, Eur. J. Inorg. Chem., 2015, 22, 3642–3648

We report here on the multiproton-multielectron electrochemical reduction of CO2 in homogeneous solution by using (TOA)6[α-SiW11O39Co(_)] (TOA = tetraoctyl ammonium ; _ = vacant position in the coordination sphere of Co) as an electrocatalyst. First, the electrochemical behavior of (TOA)6[α-SiW11O39Co(_)] was analyzed in detail by cyclic voltammetry in dichloromethane, studying the influence of the presence of protons and/or CO2. These preliminary results were further used to optimize the conditions of electrolysis in terms of reduction potentials. Analysis of the electrolysis products in the gas and liquid phases show the formation of CO and HCHO without formation of H2. Our results tend to show that the (TOA)6[α-SiW11O39Co(_)] polyoxometalate is a catalyst for CO2 electroreduction, with unique selectivity.

Covalent amphiphilic polyoxometalates for the design of biphasic microemulsion systems

V. Jallet, G. Guillemot, J. Lai, P. Bauduin, V. Nardello-Rataj, A. Proust, Chem. Commun., 2014, 50, 6610-6612.

Covalent amphiphilic polyoxometalates generated from alkylphosphonic acids have been synthesized, characterized and monitored by multinuclear NMR spectroscopy. Among them, K3H[γ–SiW10O36(C12H25PO)2], has been successfully used as surfactant for the stabilization of a Winsor I type microemulsion system.

Selective formation of epoxylimonene catalyzed by phosphonyl/arsonyl derivatives of trivacant polyoxotungstates at low temperature

O. Makrygenni,  L. Vanmairis, S. Taourit,  F. Launay,  A. Shum Cheong Sing,  A. Proust, H. Gérard, R. Villanneau. Eur. J. Inorg. Chem., 2020, 605–612

The catalytic performances of organophosphonyle/arsonyle derivatives of POMs were evaluated for the epoxidation of limonene in acetonitrile, using aqueous H2O2 as the oxidant. The use of B,a-[NaHAsW9O33{P(O)R}2]3- (R = tBu, -CH2CH2CO2H) complexes led to the complete formation of epoxylimonene at 4°C without any additional transition metal ions. The selectivity of the reaction was modulated by varying the reaction solvent, since allylic reactions were favored in ethanol. The effect of the catalyst protonation was also investigated by DFT calculations, highlighting the role of protons in the epoxidation process.

Surface pressure induced 2D-crystallization of POM-based surfactants : preparation of nanostructured thin films

L. de Viguerie, A. Mouret, H.-P. Brau, V. Nardello-Rataj, A. Proust, P. Bauduin, Cryst. Eng. Comm., 2012, 14, 8446-8453.

A polyoxometalate based surfactant shows the coexistence between monodisperse micrometric hexagonal 2D-crystallites with a liquid state monolayer at the air–water interface.

Heteropolytungstate-decorated core-shell magnetic nanoparticles: A covalent strategy for polyoxometalate-based hybrid nanomaterials

O. Makrygenni, E. Secret, A. Michel, D. Brouri, V. Dupuis, A. Proust, J.-M. Siaugue, R. Villanneau, J. Colloids Interf. Sci., 2018, 514, 49–58.

Amino-functionalized core–shell magnetic nanoparticles have been covalently grafted with polyoxometalate. These multifunctional nanocomposites have been obtained through the coupling of heteropolytungstate-based hybrids bearing carboxylic acid functions with aminopropyl functions that decorate the core–shell nanoparticles. The excellent nanostructuration of the POMs at the surface of the obtained nanoparticles have thus been directly observed by high-resolution transmission electronic microscopy (HR-TEM). Furthermore, the hyperthermia properties of these nanocomposites have been also considered as a function of the size of the magnetic core. Finally, the stability of these suspensions in organic media makes them particularly interesting in the frame of their processing or their potential use as nanocatalysts.

Pickering Emulsion Stabilized by Catalytic Polyoxometalate Nanoparticles : A New Effective Medium for Oxidation Reactions

L. Leclercq, A. Mouret, A. Proust, V. Schmitt, P. Bauduin, J.-M. Aubry, V. Nardello-Rataj, Chem. Eur. J., 2012, 18, 14352-14358.

Mixing it up a bit : Spherical nanoparticles of decyl- and dodecyltrimethylammonium cations with [PW12O40]3− formed stable Pickering emulsions in the presence of an aromatic solvent and water. This system is an efficient medium for epoxidation.

Addition of N-Heterocyclic-Carbenes to Ruthenium(VI)-Nitrido Polyoxometalate : a new route to Cyclic Guanidines

C. Besson, J.-H. Mirebeau, S. Renaudineau, S. Roland, S. Blanchard, H. Vezin, C. Courillon, A. Proust, Inorg. Chem., 2011, 50, 2501-2506.

The scope of N-atom transfer from the electrophilic ruthenium(VI) nitrido containing polyoxometalate [PW11O39RuVIN]4− has been extended to the N-heterocyclic carbene {CH2(Mes)N}2C and the coupling product {CH2(Mes)N}2CNH2+ characterized by 1H NMR and high-resolution mass spectrometry. Because guanidines display many fields of applications ranging from biology to supramolecular chemistry, this could afford an original route to the synthesis of cyclic guanidines. This also enlarges the potential of nitrido complexes in the synthesis of heterocycles, mainly illustrated in the literature through the formation of aziridines through N-atom transfer to alkenes. In the course of the reaction, the ruthenium(III)-containing polyoxometallic intermediate [PW11O39RuIII{NC{N(Mes)CH2}2}]5− has been thoroughly characterized by continuous-wave and pulsed electron paramagnetic resonance, which nicely confirms the presence of the organic moiety on the polyoxometallic framework, Ru K-edge X-ray absorption near-edge structure, and electrochemistry.

Polyoxometalates : Powerful Catalysts for Atom-Efficient Cyclopropanations

I. Boldini, G. Guillemot, A. Caselli, A. Proust, E. Gallo, Adv. Synth. Catal. 2010, 352,2365-2370.

The polyoxometalate-based catalytic cyclopropanation of olefins by EDA (EDA = ethyldiazoacetate) is reported. The outstanding catalyst productivity (TON up to 100.000) and the use of equimolar EDA/olefin ratio confer to the methodology a high sustainability. Preliminary mechanistic investigations are also discussed.

Cs9[(γ-PW10O36)2Ru4O5(OH)(H2O)4], a new all-inorganic, soluble catalyst for the efficient visible-light-driven oxidation of water

Claire Besson, Zhuangqun Huang, Yurii V. Geletii, Sheri Lense, Kenneth I. Hardcastle, Djamaladdin G. Musaev, Tianquan Lian, Anna Proust and Craig L. Hill, Chem. Commun.201046, 2784-2786

The tetraruthenium-substituted polyoxometalate Cs9[(γ-PW10O36)2Ru4O5(OH)(H2O)4] was synthesized and structurally, spectroscopically and electrochemically characterized ; it was shown to be a catalyst for visible-light-induced water oxidation.

Structural, Physicochemical, and Reactivity Properties of an All-Inorganic, Highly Active Tetraruthenium Homogeneous Catalyst for Water Oxidation

Y. V. Geletii, C. Besson, Y. H., Q. Yin, D. G. Musaev, D. Quinonero, R. Cao, K. I. Hardcastle, A. Proust, P. Kogerler, C. L. Hill, J. Am. Chem. Soc.2009131, 17360–17370

Several key properties of the water oxidation catalyst Rb8K2[{RuIV4O4(OH)2(H2O)4}(γ-SiW10O36)2] and its mechanism of water oxidation are given. The one-electron oxidized analogue [{RuVRuIV3O6(OH2)4}(γ-SiW10O36)2]11− has been prepared and thoroughly characterized.

The voltammetric rest potentials, X-ray structures, elemental analysis, magnetism, and requirement of an oxidant (O2) indicate these two complexes contain [RuIV4O6] and [RuVRuIV3O6] cores, respectively. Voltammetry and potentiometric titrations establish the potentials of several couples of the catalyst in aqueous solution, and a speciation diagram (versus electrochemical potential) is calculated. The potentials depend on the nature and concentration of counterions. The catalyst exhibits four reversible couples spanning only ca. 0.5 V in the H2O/O2 potential region, keys to efficient water oxidation at low overpotential and consistent with DFT calculations showing very small energy differences between all adjacent frontier orbitals. The voltammetric potentials of the catalyst are evenly spaced (a Coulomb staircase), more consistent with bulk-like properties than molecular ones. Catalysis of water oxidation by [Ru(bpy)3]3+ has been examined in detail. There is a hyperbolic dependence of O2 yield on catalyst concentration in accord with competing water and ligand (bpy) oxidations. O2yields, turnover numbers, and extensive kinetics data reveal several features and lead to a mechanism involving rapid oxidation of the catalyst in four one-electron steps followed by rate-limiting H2O oxidation/O2 evolution. Six spectroscopic, scattering, and chemical experiments indicate that the catalyst is stable in solution and under catalytic turnover conditions. However, it decomposes slowly in acidic aqueous solutions (pH < 1.5).