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2019



  • L. Ben Haj Hassen, S. Dhifaoui, Y. Rousselin, V. Marvaud, C. Stern, C. E. Schulz, et H. Nasri, « New insights on the electronic, magnetic, electric and molecular structure of a bis-(4-cyanopyridine) iron(III) complex with the meso-tetrakis(4-methoxyphenyl)porphyrin », Inorganica Chimica Acta, vol. 486, p. 675-683, févr. 2019.
    Résumé : We have successfully synthesized and characterized a new low-spin iron(III) bis(4-cyanopyridine) complex with a meso-porphyrin substituted in the para positions of the phenyls by the methoxy group, namely the bis(4-cyanopyridine)[(meso-tetrakis(4-metoxyphenylporphyrinato)]iron(III) trifluoromethanesulfonate chlorobenzene monosolvate complex with the formula [FeIII(TMPP)(4-CNpy)2]SO3CF3.C6H5Cl (I). This species was characterized through ultraviolet–visible, Fourier-transform infrared and Mössbauer spectroscopy as well as by SQUID magnetometry, cyclic voltammetry, and X-ray crystallography. These characterizations indicated that our synthetic heme model is a low-spin (S = 1/2) coordination compound and especially shows that the structural, electronic and the magnetic properties of complex (I) are closely dominated by the presence of the methoxy σ-donor group at the para positions of the meso-porphyrin.
    Mots-clés : Cyclic voltammetry, E-POM, Iron(III) porphyrin, Magnetic properties, X-ray Molecular structure.


  • J. Besnardiere, B. Ma, A. Torres-Pardo, G. Wallez, H. Kabbour, J. M. González-Calbet, H. J. Von Bardeleben, B. Fleury, V. Buissette, C. Sanchez, T. Le Mercier, S. Cassaignon, et D. Portehault, « Structure and electrochromism of two-dimensional octahedral molecular sieve h’-WO3 », Nature Communications, vol. 10, nᵒ 1, p. 327, janv. 2019.
    Résumé : Octahedral molecular sieves (OMS) are built of transition metal-oxygen octahedra that delimit sub-nanoscale cavities. Compared to other microporous solids, OMS exhibit larger versatility in properties, provided by various redox states and magnetic behaviors of transition metals. Hence, OMS offer opportunities in electrochemical energy harnessing devices, including batteries, electrochemical capacitors and electrochromic systems, provided two conditions are met: fast exchange of ions in the micropores and stability upon exchange. Here we unveil a novel OMS hexagonal polymorph of tungsten oxide called h’-WO3, built of (WO6)6 tunnel cavities. h’-WO3 is prepared by a one-step soft chemistry aqueous route leading to the hydrogen bronze h’-H0.07WO3. Gentle heating results in h’-WO3 with framework retention. The material exhibits an unusual combination of 1-dimensional crystal structure and 2-dimensional nanostructure that enhances and fastens proton (de)insertion for stable electrochromic devices. This discovery paves the way to a new family of mixed valence functional materials with tunable behaviors.
    Mots-clés : ERMMES, POLE 2.


  • A. Cartier, E. Levernier, V. Corcé, T. Fukuyama, A. - L. Dhimane, C. Ollivier, I. Ryu, et L. Fensterbank, « Carbonylation of Alkyl Radicals Derived from Organosilicates through Visible-Light Photoredox Catalysis », Angewandte Chemie International Edition, vol. 58, nᵒ 6, p. 1789-1793, 2019.
    Résumé : Primary, secondary, and tertiary alkyl radicals formed by the photocatalyzed oxidation of organosilicates underwent efficient carbonylation with carbon monoxide (CO) to give a variety of unsymmetrical ketones. This study introduces the possibility of radical carbonylation under a photooxidative regime.
    Mots-clés : carbonylation, CHEMBIO, MACO, photocatalysis, POLE 1, POLE 3, radicals, silicates, three-component reactions.


  • N. Daffé, J. - R. Jiménez, M. Studniarek, A. Benchohra, M. - A. Arrio, R. Lescouëzec, et J. Dreiser, « Direct Observation of Charge Transfer and Magnetism in Fe4Co4 Cyanide-Bridged Molecular Cubes », The Journal of Physical Chemistry Letters, vol. 10, nᵒ 8, p. 1799-1804, avr. 2019.
    Résumé : We have studied the zero-dimensional cubane molecular correspondent of a Prussian blue analogue Cs–Fe4Co4 at low temperature and high magnetic field by means of L-edge X-ray absorption spectroscopy and X-ray magnetic circular dichroism. We probe the magnetic and electronic structures of Fe and Co separately upon light irradiation, which allows us to observe directly the electron transfer coupled to a spin transition phenomenon within the molecular cubes and to investigate the nature of the metastable photoexcited state. The magnetic moments in the photoexcited state are found to be M = 1.3μB (Mspin = 0.59μB with large orbital moment, Morbit = 0.74μB) for low-spin FeIII and M = 1.5μB (Mspin = 1.08μB with orbital moment, Morbit = 0.41μB) for high-spin CoII at 2 K and 6.8 T. From our results, we evidence that a strong antiferromagnetic coupling between the metal ions can be ruled out.
    Mots-clés : ERMMES, POLE 2.


  • N. Fischer-Durand, D. Lizinska, V. Guérineau, B. Rudolf, et M. Salmain, « ‘Clickable’ cyclopentadienyl iron carbonyl complexes for bioorthogonal conjugation of mid-infrared labels to a model protein and PAMAM dendrimer », Applied Organometallic Chemistry, vol. 33, nᵒ 4, p. e4798, 2019.
    Résumé : Owing to the intrinsic limitations of the conventional bioconjugation methods involving native nucleophilic functions of proteins, we sought to develop alternative approaches to introduce metallocarbonyl infrared labels onto proteins on the basis of the [3?+?2] dipolar azide-alkyne cycloaddition (AAC). To this end, two cyclopentadienyl iron dicarbonyl (Fp) complexes carrying a terminal or a strained alkyne handle were synthesized. Their reactivity was examined towards a model protein and poly (amidoamine) (PAMAM) dendrimer, both carrying azido groups. While the copper (I)-catalysed azide-alkyne cycloaddition (CuAAC) proceeded smoothly with the terminal alkyne metallocarbonyl derivative, labelling by strain-promoted azide-alkyne cycloaddition (SPAAC) was less successful in terms of final coupling ratios. Infrared spectral characterization of the bioconjugates showed the presence of two bands in the 2000?cm?1 region, owing to the stretching vibration modes of the carbonyl ligands of the Fp entities.
    Mots-clés : bioconjugation, CHEMBIO, copper (I)-catalysed azide-alkyne cycloaddition, infrared spectroscopy, metallocarbonyl complex, POLE 3, strain-promoted azide-alkyne cycloaddition.
    Note Note
    <p>doi: 10.1002/aoc.4798</p>


  • F. FUS, Y. Yang, S. Lee, S. Top, M. Carriere, A. BOURON, A. Pacureanu, J. Da Silva, M. Salmain, A. vessieres, P. Cloetens, G. Jaouen, et S. BOHIC, « Intracellular localization of an osmocenyl-tamoxifen derivative in breast cancer cells revealed by synchrotron radiation X-ray fluorescence nanoimaging », Angewandte Chemie, nᵒ ja, janv. 2019.
    Résumé : We have recently developed a series of tamoxifen-like metallocifens of the group-8 metals (Fe, Ru and Os) with strong antiproliferative activity on the triple negative breast cancer cells (MDA-MB-231). This property, not observed for the organic analog 4-hydroxytamoxifen, has been associated with the unique redox behavior of metallocenic moieties, readily affording reactive quinone methides in cancer cells. To shed light on the mechanism of action of these molecules, synchrotron radiation X-ray fluorescence (SR-XRF) nanoimaging studies were performed on cells exposed to osmocenyl-tamoxifen (Oc-OH-Tam) to disclose its intracellular distribution using osmium as an intrinsic reporter. High resolution mapping of the lipophilic Oc-OH-Tam in cells, revealed its preferential accumulation in the endomembrane system encompassing endoplasmic reticulum, nuclear envelope and vesicular structures. This is consistent with the ability of the amino nitrogen chain of the compounds to be protonated at physiological pH and responsible for electrostatic interactions between Oc-OH-Tam and membranes. We propose a comprehensive scenario that provides new insight into the cellular behavior and activation of Oc-OH-Tam and advances the understanding of its mechanism of action.
    Mots-clés : bioorganometallic chemistry, breast cancer cells, CHEMBIO, elemental tomography, osmium, POLE 3, synchrotron X-ray fluorescence.
    Note Note
    <p>doi: 10.1002/ange.201812336</p>


  • D. Garnier, A. Mondal, Y. Li, P. Herson, L. - M. Chamoreau, L. Toupet, M. Buron Le Cointe, E. M. B. Moos, F. Breher, et R. Lescouëzec, « Tetranuclear [FeII2FeIII2]2+ molecular switches: [FeII(bik)2(N–)2] spin-crossover complexes containing [FeIII(Tp)(CN)3]– metalloligands as N-donor », Comptes Rendus Chimie, mai 2019.
    Résumé : Three novel mixed valence cyanide-bridged {FeIII2FeII2} square complexes were obtained through the self-assembling of [FeIII(Tp)(CN)3]- or [FeIII(Tp*)(CN)3]− cyanido building blocks with the in situ formed [FeII(bik)2(S)2] complex (Tp = hydrotris (pyrazol-1-yl)borate, Tp* = hydrotris (3,5-dimethyl-pyrazol-1-yl)borate, bik = bis(1-methylimidazol-2-yl)ketone, S = solvent). The structures of these three complexes (2, 3 and 4) are reminiscent of that of our previously published square complex {[FeIII(Tp)(CN)3]2 [FeII(bik)2]2}·[FeIII(Tp)(CN)3]2·18H2O·4CH3OH (1). They consist of cyanide-bridged square dicationic complexes, ClO4− (2 and 3) or BF4− (4) counterions and solvate molecules. The FT-IR cyanide stretching vibrations observed at νCN ≈ 2145–60 cm−1 are typical of {FeIII–CN–FeII} moieties. The investigation of the magnetic properties of 2 reveals the occurrence of spin-crossover centered at T1/2 = 227 K. The χMT variation, ca. 7 cm3 mol−1 K, reflects the complete spin-state change occurring on both {FeII(bik)(–NC)2} moieties (–NC represents the cyanido building blocks). The Slichter–Drickamer model leads to a weak cooperativity factor, Γ = 1.6 kJ mol−1 (with Γ < 2RT1/2), which reflects the gradual spin-state change. This is in agreement with the molecular structure of 2, which does not present significant intermolecular interactions. The calculated enthalpy and entropy variations associated with the spin-state equilibrium are ΔH = 24 kJ mol−1 and ΔS = 105 J K−1 mol−1. In contrast, 3 and 4 show only partial spin-crossover in the accessible temperature range (2–400 K) as the T1/2 are shifted toward higher temperatures (ca. T1/2 > 400 K). Although no photomagnetic effect is observed for 3, compound 4 shows a moderate increase in the magnetization upon irradiation at low temperature. This phenomenon is ascribed to the light-induced excited spin-state trapping (LIESST) effect. Interestingly, the complex 2 also shows a remarkable LIESST effect, which is observed with different laser lights covering the visible and near-infrared range. The resulting χMT value obtained in the photoinduced state suggests the occurrence of a ferromagnetic interaction inside the {FeIII–CN–FeII} units. Résumé Trois nouveaux complexes carrés {FeIII2FeII2} à pont cyanure et à valence mixte ont été obtenus par auto-assemblage des précurseurs cyanurés [FeIII(Tp)(CN)3]− ou [FeIII(Tp*)(CN)3]− et du complexe cationique [FeII(bik)2(S)2] formé in situ (Tp = hydrotris (pyrazol-1-yl)borate, Tp* = hydrotris (3,5-dimethyl-

    pyrazol-1-yl)borate, bik = bis(1-methylimidazol-2-yl)cétone, S = solvant). Les structures de ces trois complexes (2, 3 et 4) sont similaires à celle du complexe {[FeIII(Tp)(CN)3]2[FeII(bik)2]2}[FeIII(Tp)(CN)3]2·18H2O·4CH3OH (1) préalablement publié. Elles sont constituées de complexes carrés dicationiques à pont cyanure, de contre-ions ClO4− (2 and 3) ou BF4− (4) et de molécules de solvant. Les vibrations d’élongation des cyanures, observée en spectroscopie IR à νCN ≈ 2145–60 cm−1, sont caractéristiques d'unités {FeIII–CN–FeII}. L’étude des propriétés magnétiques de 2 révèle un équilibre de spin centré à T1/2 = 227 K. La variation du produit χMT, ca. 7 cm3 mol−1 K, traduit une conversion de spin complète sur chacune des unités {FeII(bik)(–NC)2} du carré (–NC représente le complexe précurseur cyanuré). L'analyse des données par le modèle de Slichter–Drickamer conduit à un faible facteur de coopérativité, Γ = 1.6 kJ mol−1 K (with Γ < 2RT1/2), en accord avec un changement d’état de spin graduel. Ces données sont en accord avec la structure de 2 qui ne montre pas d'interactions intermoléculaires notables. Les valeurs des variations d'enthalpie et d'entropie associées à la conversion de spin sont ΔH = 24 kJ mol−1 et ΔS = 105 J K−1 mol−1. Au contraire de 2, les composés 3 and 4 présentent seulement une conversion de spin partielle dans le domaine de température exploré (2–400 K), avec des valeurs T1/2 déplacées vers les hautes températures (ca. T1/2 > 400 K). Tandis qu'on n'observe pas d'effet photomagnétique pour 3 et seulement un faible effet dans 4, le composé 2 présente une forte augmentation de son aimantation sous irradiation à basse température. Cet effet est dû au piégeage photo-induit d'un état excité de spin (effet « LIESST », Light-Induced Excited Spin-State Trapping). Il est observé avec différentes sources laser couvrant le spectre visible et le proche infrarouge. Les valeurs de χMT obtenues dans l’état photo-induit suggèrent la présence d'une interaction ferromagnétique au sein de la paire {FeIII–CN–FeII}.
    Mots-clés : ERMMES, POLE 2.


  • M. Girardi, D. Platzer, S. Griveau, F. Bedioui, S. Alves, A. Proust, et S. Blanchard, « Assessing the Electrocatalytic Properties of the Cp*RhIII2+-Polyoxometalate Derivative [H2PW11O39RhIIICp*(OH2)]3– towards CO2 Reduction », European Journal of Inorganic Chemistry, vol. 2019, nᵒ 3-4, p. 387-393, 2019.
    Résumé : Storage of electricity produced intermittently by renewable energy sources is a societal issue. Besides the use of batteries and supercapacitors, conversion of excess electricity into chemical energy is also actively investigated. The conversion of CO2 to fuel or fuel precursors is an option that requires the use of a catalyst to overcome the high activation energy barrier. Of molecular catalysts, metal complexes with polypyridyl ligands are well represented, among which the [Cp*Rh(bpy)Cl]+ and [M(bpy)(CO)3X] (M = Re, Mn) complexes. As redox non-innocent ligand, the bipyridine ligand is generally involved in the reduction mechanisms. It is thus tempting to replace it by other redox non-innocent ligands such as vacant polyoxometalates (POMs). We have thus prepared [α-H2PW11O39RhIIICp*(OH2)]3– which is closely related to [Cp*RhIII(bpy)Cl]+ by substitution of the monovacant [PW11O39]7– Keggin-type POM for the bipyridine ligand. Its activity towards CO2 reduction has been assessed in acetonitrile in the presence of water. Compared to [Cp*Rh(bpy)Cl]+ that produces formate selectively over CO and H2, the POM derived catalyst favors proton reduction over CO2 reduction.
    Mots-clés : Carbon dioxide fixation, CSOB, E-POM, Non-innocent ligands, Polyoxometalates, Redox chemistry.
    Pièce jointe Full Text PDF 974.1 ko (source)


  • A. Harbi, H. Moutaabbid, Y. Li, C. Renero-Lecuna, M. Fialin, Y. Le Godec, S. Benmokhtar, et M. Moutaabbid, « The effect of cation disorder on magnetic properties of new double perovskites La2NixCo1-xMnO6 (x = 0.2–0.8) », Journal of Alloys and Compounds, vol. 778, p. 105-114, mars 2019.
    Résumé : Solid solutions of new double perovskite oxides La2NixCo1-xMnO6 (x = 0.2, 0.25, 0.5, 0.75, 0.8) were synthesized by solid-state reaction method. The X-ray powder diffraction data show that all the compounds crystallize in the monoclinic structure with space group P21/n at room temperature. The elementary composition of the powders was determined by the electron Probe Microanalysis. Raman and IR spectra show strong bands at (520, 650 cm−1) and (426, 600 cm−1) respectively, attributed to the stretching vibration of Ni/Co-O and Mn-O bonds in the structure. The magnetic studies for all the compounds have been performed in both DC and AC magnetic fields in the temperature range from 2 to 300 K. All samples exhibit a main paramagnetic to ferromagnetic (PM-FM) transition between 232 K and 260 K, and their Curie temperature increases rapidly with increasing x values. Three samples with x = 0.2, 0.25 and 0.5 respectively display also a secondary PM-FM transition between 200 K and 208 K. The thermal variation of out of phase component of AC susceptibility presents also frequency-dependent transitions between 65 K and 110 K unfolding the existence of super-paramagnetic mono-domains in all samples. The band gap energy has been calculated and revealing semiconductor behavior for all samples.
    Mots-clés : ERMMES, POLE 2.


  • « 15 Silicates in Photocatalysis », in Photocatalysis in Organic Synthesis, 2019ᵉ éd., B. König, Éd. Stuttgart: Georg Thieme Verlag, 2019.
    Mots-clés : CHEMBIO, MACO, POLE 1, POLE 3.


  • C. M. Kronfel, C. V. Hernandez, J. P. Frick, L. S. Hernandez, A. Gutu, J. A. Karty, M. N. Boutaghou, D. M. Kehoe, R. B. Cole, et W. M. Schluchter, « CpeF is the bilin lyase that ligates the doubly linked phycoerythrobilin on β-phycoerythrin in the cyanobacterium <i>Fremyella diplosiphon</i> », Journal of Biological Chemistry, p. jbc.RA118.007221, janv. 2019.


  • D. Lesage, S. Mezzache, Y. Gimbert, H. Dossmann, et J. - C. Tabet, « Extended kinetic method and RRKM modeling to reinvestigate proline’s proton affinity and approach the meaning of effective temperature », European Journal of Mass Spectrometry, p. 146906671882205, janv. 2019.


  • O. Makrygenni, D. Brouri, A. Proust, F. Launay, et R. Villanneau, « Immobilization of polyoxometalate hybrid catalysts onto mesoporous silica supports using phenylene diisothiocyanate as a cross-linking agent », Microporous and Mesoporous Materials, vol. 278, p. 314-321, avr. 2019.
    Résumé : The hybrid derivative of heteropolytungstate bearing two aniline groups, namely (nBu4N)3[NaHPW9O34{As(O)C6H4NH2}2], was post-functionalized in the presence of 1,4-phenylene diisothiocyanate (PDITC). The resulting molecular moiety was characterized by IR, 1H and 31P NMR spectroscopy. In a second step, this post-functionalized hybrid of polyoxometalate was covalently grafted onto the surface of an amino-functionalized SBA-15 silica by means of the formation of thiourea bonds. This simple and efficient strategy of immobilization did not require the use of a coupling agent and was performed in mild reaction conditions. Various physicochemical techniques (13C and 31P CPMAS NMR spectroscopies, XPS, XRF, HR-TEM microscopy and N2 sorption) contributed to the full characterization of the supported catalyst. In addition HR-TEM was found to be an essential technique for the identification of the polyoxometalate units inside the pores of SBA-15. Finally, the catalytic performances of the supported polyoxometalates were evaluated in the epoxidation of cyclooctene with aqueous H2O2 in acetonitrile at 50 °C.
    Mots-clés : Anchored homogeneous catalysts, E-POM, Epoxidation catalysis, Functionalized mesoporous silica materials, Polyoxometalate hybrids.


  • C. Medena, F. Calogero, Q. Lemoine, C. Aubert, E. Derat, L. Fensterbank, G. Gontard, O. Khaled, N. Vanthuyne, J. Moussa, C. Ollivier, M. Petit, et M. Barbazanges, « A HELIXOL-Derived Bisphosphinite Ligand: Synthesis and Application in Gold-Catalyzed Enynes Cycloisomerization », European Journal of Organic Chemistry, vol. 2019, nᵒ 11, p. 2129-2137, 2019.
    Résumé : The synthesis, optical resolution through derivatization, characterization, and utilization of a new helical bis(phosphinite gold) complex derived from HELIXOL are described. By using an efficient cobalt catalyst, neither irradiation nor high catalytic loading was required to access the helicene of interest. The latter was phosphorylated to afford a new chiral ligand that was studied. Especially, treatment with AuCl(SMe2) gives a dinuclear gold complex that was used in cycloisomerization reactions.
    Mots-clés : ARC, Chirality, Enyne Cycloisomerization, Helicene, Homogeneous catalysis, MACO, Phosphinite, POLE 1.
    Pièce jointe Full Text PDF 1.5 Mo (source)


  • T. Neva, T. Carmona, J. M. Benito, C. Przybylski, C. Ortiz Mellet, F. Mendicuti, et J. M. García Fernández, « Dynamic Control of the Self-Assembling Properties of Cyclodextrins by the Interplay of Aromatic and Host-Guest Interactions », Frontiers in Chemistry, vol. 7, p. 72, 2019.
    Résumé : The presence of a doubly-linked naphthylene clip at the O-2I and O-3II positions in the secondary ring of -cyclodextrin (CD) derivatives promoted their self-assembly into head-to-head supramolecular dimers in which the aromatic modules act either as cavity extension walls (if the naphthalene moiety is 1,8-disubstituted) or as folding screens that separate the individual CD units (if 2,3-disubstituted). Dimer architecture is governed by the conformational properties of the monomer constituents, as determined by NMR, fluorescence, circular dichroism and computational techniques. In a second supramolecular organization level, the topology of the assembly directs host-guest interactions and, reciprocally, guest inclusion impacts the stability of the supramolecular edifice. Thus, inclusion of adamantane carboxylate, a well-known CD cavity-fitting guest, was found to either preserve the dimeric arrangement, leading to multicomponent species, or elicit dimer disruption. The ensemble of results highlights the potential of the approach to program self-organization and external stimuli responsiveness of CD devices in a controlled manner while keeping full diastereomeric purity.
    Mots-clés : CSOB, POLE 3.


  • W. X. C. Oliveira, W. D. do Pim, C. B. Pinheiro, Y. Journaux, M. Julve, et C. L. M. Pereira, « Monitoring the hydrogen bond net configuration and the dimensionality of aniline and phenyloxamate by adding 1H-pyrazole and isoxazole as substituents for molecular self-recognition », CrystEngComm, vol. 21, nᵒ 17, p. 2818-2833, avr. 2019.
    Résumé : This work describes the synthesis and characterization of a new class of oxamic acid derivatives containing pyrazole and isoxazole as substituents to investigate their ability to form hydrogen bonds aiming at applying them in crystal engineering and molecular self-recognition. In this respect, we report a new synthesis of 2-(4-nitrophenyl)-1,3-propanedial (1) in high yield using SOCl2 as a chlorinating agent. The new oxamic esters 4-(1H-pyrazol-4-yl)phenylene-N-(ethyloxamate) (2d) and 4-(1,2-oxazol-4-yl)phenylene-N-(ethyloxamate) (3d) were prepared from 1. The synthetic route consists of the cyclisation of 1 either with hydrazine to afford 4-(-aminophenyl)-1H-pyrazole (2a) or with hydroxylamine to obtain the isoxazole-based molecule 4-(4-nitrophenyl)-1,2-oxazole (3a). The reduction of 2a and 3a was carried out in an acidic/tin solution to yield 4-(4-ammoniophenyl)-1H-pyrazol-2-ium trichlorostannate(II) chloride monohydrate (2b) and 4-(4-ammoniophenyl)-1,2-oxazole hexachlorostannate(IV) (3b). Basic extraction of 3b provided 4-(4-aminophenyl)-1,2-oxazole (3c). The reduction of 2a to 4-(4-aminophenyl)-1H-pyrazole (2c) was achieved by means of hydrazine associated with supported palladium on carbon. The condensation of 2c and 3c with ethyl chlorooxoacetate delivers oxamic esters 2d and 3d. In n-tetrabutylammonium hydroxide solution 2d is fully hydrolyzed, obtaining the n-tetrabutylammonium salt of 4-(1H-pyrazole-4-yl)phenylene-N-oxamate as a hemihydrate (2e). The low stability of isoxazole molecules in basic solutions was proved by crystallizing the n-tetrabutylammonium salt of 1-cyano-1-(4-nitrophenyl)-2-oxoethanide (3f) (obtained by cleavage of 3d with n-Bu4NOH) and preparing its conjugated acid 2-(4-nitrophenyl-3-oxopropanenitrile (3e). The structures of 2b, 3b, 3d and 2e were solved by single crystal X-ray diffraction techniques. The analysis of their crystal packing reveals hydrogen bond features compatible for all compounds as well as some differences depending on the pH of the crystallization solution and the presence or absence of the oxamate group due to the increase of hydrogen bond donors and acceptors.
    Mots-clés : ERMMES, POLE 2.
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  • C. Przybylski, V. Bonnet, et R. R. Vivès, « A microscale double labelling of GAG oligosaccharides compatible with enzymatic treatment and mass spectrometry », Chemical Communications, vol. 55, nᵒ 29, p. 4182-4185, 2019.


  • C. Przybylski, H. Ramoul, V. Bonnet, M. Abad, et N. Jarroux, « Harnessing Polyisobutylene by Rotaxanation with γ-Cyclodextrin: Opportunities for Making Smart Molecular Necklaces », Macromolecular Chemistry and Physics, vol. 220, nᵒ 5, p. 1800502, mars 2019.
    Résumé : Abstract A new type of polyrotaxane based on the threading of ?-cyclodextrins (?-CDs) along a highly hydrophobic polymer, polyisobutylene (PIB), is successfully prepared and finely characterized. The used radical coupling associated with tuned reaction time and temperature leads to a fast and controlled necklace synthesis with low reagent consumption. Synthesis exhibits appealing conversion and threading rates with almost 100% and 62?73%, respectively. A combination of well-established SEC and NMR techniques, with a more forefront MALDI-TOF MS approach, provides details on the original PIB and the resulting polyrotaxanes (M w, M n, PDI, and average number of ?-CD threaded). Interestingly, tetramethylguanidinium-2-(4-hydroxyphenylazo)benzoate in DMF for MALDI analysis is revealed as a suitable matrix to overcome solubility troubles widely observed with PIB. Moreover, rotaxanation appears as an alternative to the grafting of polar groups to modify/handle hydrophobic polymers. Such an approach offers new opportunities to achieve the synthesis, with unambiguous evidence, of new supramolecular necklaces based on highly hydrophobic polymers.
    Mots-clés : CSOB, cyclodextrins, mass spectrometry, POLE 3, polyisobutylene, polyrotaxane, radical coupling.
    Note Note
    <p>doi: 10.1002/macp.201800502</p>


  • I. Seffouh, C. Przybylski, A. Seffouh, R. El Masri, R. R. Vivès, F. Gonnet, et R. Daniel, « Mass spectrometry analysis of the human endosulfatase Hsulf-2 », Biochemistry and Biophysics Reports, vol. 18, p. 100617, 2019.
    Résumé : The human 6-O-endosulfatases HSulf-1 and -2 catalyze the region-selective hydrolysis of the 6-O-sulfate group of the glucosamine residues within sulfated domains of heparan sulfate, thereby ensuring a unique and original post-biosynthetic modification of the cell surface proteoglycans. While numerous studies point out the role of HSulf-2 in crucial physiological processes as well as in pathological conditions particularly in cancer, its structural organization in two chains and its functional properties remain poorly understood. In this study, we report the first characterization by mass spectrometry (MS) of HSulf-2. An average molecular weight of 133,115 Da was determined for the whole enzyme by MALDI-TOF MS, i.e. higher than the naked amino acid backbone (98,170 Da), highlighting a significant contribution of post-translational modifications. The HSulf-2 protein sequence was determined by Nano-LC-MS/MS, leading to 63% coverage and indicating at least four N-glycosylation sites at Asn 108, 147, 174 and 217. These results provide a platform for further structural investigations of the HSulf enzymes, aiming at deciphering the role of each chain in the substrate binding and specificities and in the catalytic activities.
    Mots-clés : 6--Endosulfatase, CSOB, Formylglycine, Heparan sulfate, HSulf-2, Mass spectrometry, POLE 3, Sulfatase.


  • H. Z. Shirley Lee, F. Chau, S. Top, G. Jaouen, A. Vessières, E. Labbé, et O. Buriez, « New mechanistic insights into osmium-based tamoxifen derivatives », Electrochimica Acta, 2019.
    Résumé : The electrochemical behavior of osmociphenol (3, Oc-OH), an organometallic osmium-based anticancer drug candidate, has been investigated by cyclic voltammetry in the absence and presence of lutidine used as a base model. Osmociphenol exhibited spontaneous deprotonation of the phenol function upon oxidation of the osmocene moiety due to its high acidity. In the presence of lutidine, a base-dependent and different electrochemical behavior was observed at low scan rates indicating a second oxidation step leading to the corresponding cationic quinone methide precursor (3b+). However, compared to ruthenocene derivatives, the stability of 3b+ prevented its conversion into quinone methide as the final and stable complex. Despite differences in their oxidative processes, osmociphenol and ruthenociphenol derivatives exhibit similar biological activities.
    Mots-clés : Anti-cancer, Bioorganometallic, CHEMBIO, Cyclic voltammetry, Osmium, POLE 3, Tamoxifen.


  • C. Sonnendecker, S. Thürmann, C. Przybylski, F. D. Zitzmann, N. Heinke, Y. Krauke, K. Monks, A. A. Robitzki, D. Belder, et W. Zimmermann, « Large‐Ring Cyclodextrins as Chiral Selectors for Enantiomeric Pharmaceuticals », Angewandte Chemie International Edition, 2019.


  • A. Vivien, M. Guillaumont, L. Meziane, C. Salzemann, C. Aubert, S. Halbert, H. Gérard, M. Petit, et C. Petit, « Role of Oleylamine Revisited: An Original Disproportionation Route to Monodispersed Cobalt and Nickel Nanocrystals », Chemistry of Materials, vol. 31, nᵒ 3, p. 960-968, févr. 2019.
    Résumé : Herein is highlighted an original disproportionation mechanism for the formation of hexagonal closed packed cobalt nanoparticles starting from low-valent cobalt complexes. By coupling experimental and theoretical studies, we demonstrate that oleylamine promotes the disproportionation of the starting metal complexes and controls the growth of the nanocrystals, in contrast to the role of reducing reagents proposed elsewhere. We also decipher the sensitivity of the synthesis in regard to the nature of the phosp

    hine and of the halogen ligands in the starting cobalt precursors. Understanding of the mechanism allows the development of a less expensive and less toxic synthesis of these nanoparticles by decreasing the amount of oleylamine in alkane solvents. Finally, an extension of this process is presented and allows reaching size- and shape-controlled nanosphere and nanorod nickel nanoparticles.
    Mots-clés : MACO, POLE 1.


  • Y. Wang, P. Pigeon, S. Top, J. García, C. Troufflard, I. Ciofini, M. J. McGlinchey, et gerard jaouen, « Atypical lone pair-π interaction with quinone methides in a series of imido-ferrociphenol anticancer drug candidates », Angewandte Chemie International Edition, nᵒ ja, 2019.
    Résumé : Ferrociphenols, especially those possessing a heterocycle at the terminus of an aliphatic chain, display strong anticancer activity via a novel redox mechanism that generates active metabolites such as quinone methides (QMs). X-ray crystallography and UV-Vis spectroscopy reveal that the specific lone pair (lp)-π interaction between a carbonyl group of the imide and the quinone motif of the QM plays an important role in the exceptional cytotoxic behaviour of their imido-ferrociphenol precursors. This intramolecular lp-π interaction markedly enhanced the stability of the QMs and lowered the pKa values of the corresponding phenolates. As the first example of such a non-covalent interaction that stabilizes QMs remotely, it not only expands the scope of the lp-π interaction in supramolecular chemistry, but also represents a new mode of stabilization of a QM. This unprecedented application of lp-π interactions in imido-ferrociphenol anticancer drug candidates may also have great potential in drug discovery and organocatalyst design.
    Mots-clés : antitumor agents, bioorganometallics, CHEMBIO, ferrocifen, non-covalent interactions, POLE 3, quinones.
    Note Note
    <p>doi: 10.1002/anie.201902456</p>

2018



  • L. Bacri, H. Mamad-Hemouch, C. Przybylski, B. Thiebot, G. Patriarche, N. Jarroux, et J. Pelta, « Biomimetic ion channels formation by emulsion based on chemically modified cyclodextrin nanotubes », Faraday Discussions, 2018.


  • M. Barbazanges et L. Fensterbank, « The Invention of New Methodologies: An Opportunity for Dating Natural Products », Synlett, août 2018.
    Résumé : This Account surveys almost two decades of methodological developments and their straightforward applications to the total synthesis of simple natural products. The main directions covered include radical chemistry and cascades, electrophilic catalysis based on coinage metals, and asymmetric synthesis based on bis(sulfoxides) auxiliaries. 1 Introduction 2 Radical Cascades 2.1 N-Cyanamides 2.2 Homolytic Substitution at Sulfur Atom to Give Sultines 3 Electrophilic Catalysis Based on Platinum(II) and Gold(I) Complexes 4 From Alkylydene Bis(sulfoxides) to Chiral Carboxylic Acids 5 Conclusion and Perspectives
    Mots-clés : asymmetric synthesis, bis(sulfoxides), gold catalysis, Key words radical chemistry, MACO, natural products, POLE 1, total synthesis.
    Pièce jointe Full Text PDF 450.4 ko (source)


  • P. Barbier Saint Hilaire, U. M. Hohenester, B. Colsch, J. - C. Tabet, C. Junot, et F. Fenaille, « Evaluation of the High-Field Orbitrap Fusion for Compound Annotation in Metabolomics », Analytical Chemistry, vol. 90, nᵒ 5, p. 3030-3035, mars 2018.


  • C. K. Barik, R. Ganguly, Y. Li, C. Przybylski, M. Salmain, et W. K. Leong, « Embedding a Ruthenium-Based Structural Mimic of the [Fe]-Hydrogenase Cofactor into Papain », Inorganic Chemistry, vol. 57, nᵒ 19, p. 12206-12212, sept. 2018.
    Mots-clés : CHEMBIO, CSOB, POLE 3.


  • P. Bayat, D. Gatineau, D. Lesage, V. Robert, A. Martinez, et R. B. Cole, « Investigation of Hemicryptophane Host-Guest Binding Energies Using High-Pressure Collision-Induced Dissociation in Combination with RRKM Modeling », Journal of The American Society for Mass Spectrometry, nov. 2018.


  • P. Bayat, D. Lesage, et R. B. Cole, « Low-energy collision-induced dissociation (low-energy CID), collision-induced dissociation (CID), and higher energy collision dissociation (HCD) mass spectrometry for structural elucidation of saccharides and clarification of their dissolution mechanism i », Journal of Mass Spectrometry, vol. 53, nᵒ 8, p. 705-716, 2018.

  • M. Ben Haddada, M. Salmain, et S. Boujday, « Gold colloid-nanostructured surfaces for enhanced piezoelectric immunosensing of staphylococcal enterotoxin A », Sensors and Actuators B: Chemical, vol. 255, nᵒ 2, p. 1604-1613, 2018.


  • S. ben Moussa, A. Mehri, M. Gruselle, P. Beaunier, G. Costentin, et B. Badraoui, « Combined effect of magnesium and amino glutamic acid on the structure of hydroxyapatite prepared by hydrothermal method », Materials Chemistry and Physics, vol. 212, p. 21-29, juin 2018.
    Résumé : Magnesium modified calcium hydroxyapatite of different Mg/Ca compositions have been synthesized using the hydrothermal method in the presence of glutamic acid. The resulting materials have been characterized by X-ray powder diffraction, chemical analysis, IR Spectroscopy and Transmission Electron Microscopy (TEM). X-ray diffraction analysis shows that the resulting materials consist of a single phase having an apatitic structure. IR spectroscopy highlights the presence of carboxylic groups for the organic moieties grafted onto the apatitic surface. The surface properties of apatite samples are determined.
    Mots-clés : Apatite surface, ARC, Glutamic acid, Hybrid compound, Hydrothermal method, POLE 1.

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  • L. Benda, B. Doistau, B. Hasenknopf, et G. Vives, « Synthesis and Guest Recognition of Switchable Pt-Salphen Based Molecular Tweezers », Molecules, vol. 23, nᵒ 5, p. 990, avr. 2018.


  • B. Bertrand, K. Passador, C. Goze, F. Denat, E. Bodio, et M. Salmain, « Metal-based BODIPY derivatives as multimodal tools for life sciences », Coordination Chemistry Reviews, vol. 358, p. 108-124, 2018.
    Résumé : Nowadays, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene – better known as BODIPY – is at the forefront of fluorophores for life sciences. Indeed, its high brightness, its tunable excitation and emission wavelengths along with its high chemical and photochemical stability draw more and more the interest of researchers. In the last decade, chemists have taken advantage of the versatility of the synthesis of BODIPY to design sophisticated objects. This review focuses on the different recent studies dealing with the conception of metal-based-BODIPY derivatives for medical purposes. More precisely, emphasis is put on the use of BODIPY derivatives for the elaboration of BODIPY-based theranostics, multimodal imaging probes, and photodynamic therapy sensitizers.
    Mots-clés : Bimodal imaging, BODIPY, CHEMBIO, Fluorescence, Metal-based drugs, Photodynamic therapy, POLE 3, Theranostics.


  • P. Biais, P. Beaunier, F. Stoffelbach, et J. Rieger, « Loop-stabilized BAB triblock copolymer morphologies by PISA in water », Polymer Chemistry, vol. 9, nᵒ 35, p. 4483-4491, sept. 2018.
    Résumé : A straightforward strategy to synthesize loop-stabilized particles in water via PISA is developed. These particular structures can in theory be obtained through the synthesis of amphiphilic BAB triblock copolymers, starting from a hydrophilic middle block A, which is chain extended in an aqueous PISA process with two hydrophobic external blocks B. For this purpose, symmetrical bifunctional poly(N,N-dimethylacrylamide) macroRAFT agents with a central benzoic acid group and an alkyl chain as the Z group are used in the aqueous dispersion polymerization of diacetone acrylamide. For the first time, stable BAB flower-like particles are formed via PISA in pure water. It is shown that the colloidal stability and the resulting particle morphology (spheres, worms, vesicles) strongly depend on the degree of ionization of the central charge in the stabilizer loop, and thus on the pH at which PISA is performed. Moreover, the influence of the length of the alkyl Z group (dodecyl and butyl alkyl chains) on the colloidal stability is studied.
    Mots-clés : POLE 4, POLYMERES.
    Pièce jointe Full Text PDF 1.8 Mo (source)


  • F. A. Black, A. Jacquart, G. Toupalas, S. Alves, A. Proust, I. P. Clark, E. A. Gibson, et G. Izzet, « Rapid photoinduced charge injection into covalent polyoxometalate–bodipy conjugates », Chemical Science, vol. 9, nᵒ 25, p. 5578-5584, 2018.
    Mots-clés : CSOB, E-POM, POLE 2, POLE 3.


  • V. N. Bochatay, F. Chemla, F. Ferreira, O. Jackowski, et A. Pérez-Luna, « β‐Amino Propargylic Fluorides through Stereoselective Electrophilic Fluorodesilylation of 4‐Amino‐1‐allenylsilanes - Bochatay - 2018 - European Journal of Organic Chemistry - Wiley Online Library », European Journal of Organic Chemistry, p. 3862, 2018.


  • B. Brahim, J. - C. Tabet, et S. Alves, « Positive and negative ion mode comparison for the determination of DNA/peptide noncovalent binding sites through the formation of “three-body” noncovalent fragment ions », European Journal of Mass Spectrometry, vol. 24, nᵒ 1, p. 168-177, 2018.


  • N. Bridonneau, P. Quatremare, H. J. von Bardeleben, J. - L. Cantin, S. Pillet, E. - E. Bendeif, et V. Marvaud, « Direct Evidence of a Photoinduced Electron Transfer in Diluted “Molybdenum-Copper” Molecular Compounds », European Journal of Inorganic Chemistry, vol. 2018, nᵒ 3-4, p. 370-377, janv. 2018.
    Résumé : For the first time, direct evidence of a photoinduced intramolecular electron transfer has been found in the “molybdenum-copper“ family of cyanide complexes that corresponds to a [MoIV–CuII]→[MoV–CuI] transition. The design and synthesis of a diluted molecular system, [Mo(Zn(1–x)Cux)2-tren] (x = 0, ε, 1, 5 and 10 %, , with ε corresponding to ppm ratio), viewed as new model compounds, have allowed good characterization of the metastable states involved in the process and provided evidence for two different mechanisms. By using squid magnetometry, EPR spectroscopy and X-ray diffraction, the results of this study have confirmed not only the photoinduced electron transfer, but also supports the light-induced excited spin state trapping effect centred on the molybdenum, thought to be due to the presence of a high-spin state (S = 1). This article provides a better understanding of the photomagnetic behaviour in Mo-Cu complexes and reveals the importance of orbital overlap to differentiate the two effects.
    Mots-clés : Copper, E-POM, Electron transfer, Magentic properties, Molybdenum, Photomagnetism, POLE 2, Spin transition.
    Pièce jointe Full Text PDF 1.7 Mo (source)


  • R. Brisse, D. Guianvarc'h, C. Mansuy, S. Sagan, D. Kreher, L. Sosa-Vargas, L. Hamitouche, V. Humblot, I. Arfaoui, V. Labet, C. Paris, C. Petit, et A. - J. Attias, « Probing the in-air growth of large area of 3D functional structures into a 2D supramolecular nanoporous network », Chemical Communications, vol. 54, nᵒ 72, p. 10068-10071, 2018.


  • T. Buchecker, P. Schmid, S. Renaudineau, O. Diat, A. Proust, A. Pfitzner, et P. Bauduin, « Polyoxometalates in the Hofmeister series », Chemical Communications, vol. 54, nᵒ 15, p. 1833-1836, févr. 2018.
    Résumé : We propose a simple experimental procedure based on the cloud point measurement of a non-ionic surfactant as a tool for (i) estimating the super-chaotropic behaviour of polyoxometalates (POMs) and for (ii) establishing a classification of POMs according to their affinity towards polar surfaces.
    Mots-clés : E-POM.


  • X. Callies, E. Ressouche, C. Fonteneau, G. Ducouret, S. Pensec, L. Bouteiller, et C. Creton, « Effect of the Strength of Stickers on Rheology and Adhesion of Supramolecular Center-Functionalized Polyisobutenes », Langmuir, vol. 34, nᵒ 42, p. 12625-12634, oct. 2018.
    Résumé : In order to systematically investigate the effect of the strength of the supramolecular interactions on the debonding properties of associative polymers, a series of model systems have been characterized by probe-tack tests. These model materials, composed of linear and low dispersity poly(isobutylene) chains (Mn ≈ 3 kg/mol) center-functionalized by a single bis-urea sticker, are able to self-assemble by four hydrogen bonds. Three types of stickers are used in the present study: a bis-urea with a methylene diphenyl (MDI) spacer, a bis-urea with a tolyl (TOL) spacer, and a bis-urea with a xylyl (XYL) spacer. In order to investigate the influence of stickers in depth, both the nanostructure of the materials and the linear rheology were investigated by small-angle X-ray scattering (SAXS) and oscillatory shear, respectively. For two types of stickers (TOL and XYL), the association of polymers via hydrogen bonds induces the formation of bundles of rodlike aggregates at room temperature and the behavior of a soft elastic material was observed. For bis-urea MDI, no structure is detected by SAXS and a Newtonian behavior is observed at room temperature. In probe-tack experiments, all these materials show a cohesive mode of failure, a signature of flowing materials as previously observed for tri-urea center-functionalized poly(butylacrylate) (PnBA3U). However, XYL center-functionalized polyisobutene shows much higher debonding energies than PnBA3U, revealing the importance of the strength of noncovalent bonds in the scission/recombination dynamics. On the basis of the analysis of the debonding images, this effect is discussed via the mechanical behavior at large deformation.
    Mots-clés : POLE 4, POLYMERES.


  • N. Chahin, L. A. Uribe, A. M. Debela, S. Thorimbert, B. Hasenknopf, M. Ortiz, I. Katakis, et C. K. O'Sullivan, « Electrochemical primer extension based on polyoxometalate electroactive labels for multiplexed detection of single nucleotide polymorphisms », Biosensors and Bioelectronics, vol. 117, p. 201-206, 2018.
    Résumé : Polyoxymetalates (POMs) ([SiW11O39{Sn(CH2)2CO)}]4- and [P2W17O61{Sn(CH2)2CO)}]6-) were used to modify dideoxynucleotides (ddNTPs) through amide bond formation, and applied to the multiplexed detection of single nucleotide polymorphisms (SNPs) in an electrochemical primer extension reaction. Each gold electrode of an array was functionalised with a short single stranded thiolated DNA probe, specifically designed to extend with the POM-ddNTP at the SNP site to be interrogated. The system was applied to the simultaneous detection of 4 SNPs within a single stranded 103-mer model target generated using asymmetric PCR, highlighting the potential of POM-ddNTPs for targeted, multiplexed SNP detection. The four DNA bases were successfully labelled with both ([SiW11O39{Sn(CH2)2CO)}]4- and [P2W17O61{Sn(CH2)2CO)}]6-), and [SiW11O39{Sn(CH2)2CO)}]4- demonstrated to be the more suitable due to its single oxidation peak, which provides an unequivocal signal. The POM-ddNTP enzymatically incorporated to the DNA anchored to the surface was visualised by AFM using gold coated mica. The developed assay has been demonstrated to be highly reproducible, simple to carry out and with very low non-specific background signals. Future work will focus on applying the developed platform to the detection of SNPs associated with rifampicin resistance in real samples from patients suffering from tuberculosis.
    Mots-clés : CHEMBIO, Electrochemical primer extension reaction (éPEX), Multiplexed electrochemical detection, POLE 3, Polyoxometalate-labelled ddNTPs, SNP detection.


  • L. Chang, N. Klipfel, L. Dechoux, et S. Thorimbert, « A solvent-free, base-catalyzed domino reaction towards trifluoromethylated benzenes from bio-based methyl coumalate », Green Chemistry, vol. 20, nᵒ 7, p. 1491-1498, 2018.
    Résumé : A novel, efficient, and environmentally compatible method for CF3-substituted benzene production is reported. It sources a bio-based feedstock, employs tBuOK as a catalyst, and is solvent-free. This regioselective approach provides various trifluoromethyl benzenes in good to excellent yields, without any extra oxidant or special care. CO2 and water are the only byproducts of this process, and the reaction conditions can scale up to gram quantities. The transformation involves an unprecedented tBuOK-catalyzed domino process, and features Michael addition/6[small pi]-electrocyclic ring opening/[1,5]-H shift/carba-6[small pi]-electrocyclic ring closure/decarboxylative aromatization reactions.
    Mots-clés : CHEMBIO, POLE 3.


  • T. F. C. Cruz, C. A. Figueira, J. C. Waerenborgh, L. C. J. Pereira, Y. Li, R. Lescouëzec, et P. T. Gomes, « Synthesis, characterization and magnetism of homoleptic bis(5-aryl-2-iminopyrrolyl) complexes of iron(II) and cobalt(II) », Polyhedron, vol. 152, p. 179-187, 2018.


  • de Jesús Cázares-Marinero José, Przybylski Cédric, et Salmain Michèle, « Proteins as Macromolecular Ligands for Metal-Catalysed Asymmetric Transfer Hydrogenation of Ketones in Aqueous Medium », European Journal of Inorganic Chemistry, vol. 2018, nᵒ 12, p. 1383-1393, 2018.
    Résumé : Biohybrid catalysts resulting from the dative anchoring of half-sandwich organometallic complexes [M(arene)(H2O)x(Cl)y]n+ (M = RuII, arene = ?6-benzene, p-cymene or mesitylene; M = IrIII, RhIII, arene = ?5-Cp*; x = 1?3, y = 0?2, n = 0?2) to bovine beta-lactoglobulin (?LG) or hen egg white lysozyme showed unprecedented behaviour. These constructs were shown to catalyse the asymmetric transfer hydrogenation of aryl ketones in water with sodium formate as hydrogen donor at a much faster rate than the complexes alone. Full conversion of the benchmark substrate 2,2,2-trifluoroacetophenone was reached with an ee of 86?% for the most selective biohybrid. Surprisingly, even the crude biohybrid gave a good ee despite the presence of non-protein-bound metal species in the reaction medium. Other aryl ketones were reduced in the same way, and the highest ee was obtained for ortho-substituted acetophenone derivatives. Furthermore, treatment of ?LG with dimethyl pyrocarbonate resulted in a noticeable decrease of the activity and selectivity of the biohybrid, indicating that the sole accessible histidine residue (His146) was probably involved in the coordination and activation of Ru(benzene). This work underscores that protein scaffolds are efficient chiral ligands for asymmetric catalysis. The use of sodium formate instead of dihydrogen makes this approach safe, inexpensive and environmentally friendly.
    Mots-clés : Artificial metalloenzymes, Asymmetric catalysis, CHEMBIO, CSOB, Hydrogenation, Mass spectrometry, POLE 3, Ruthenium.
    Note Note
    <p>doi: 10.1002/ejic.201701359</p>


  • K. de la Vega-Hernández, E. Romain, A. Coffinet, K. Bijouard, G. Gontard, F. Chemla, F. Ferreira, O. Jackowski, et A. Perez-Luna, « Radical Germylzincation of α-Heteroatom-Substituted Alkynes », Journal of the American Chemical Society, vol. 140, nᵒ 50, p. 17632-17642, déc. 2018.
    Résumé : The regio- and stereoselective addition of germanium and zinc across the C–C triple bond of nitrogen-, sulfur-, oxygen-, and phosphorus-substituted terminal and internal alkynes is achieved by reaction with a combination of R3GeH and Et2Zn. Diagnostic experiments support a radical-chain mechanism and the β-zincated vinylgermanes that show exceptional stability are characterized by NMR spectroscopy and X-ray crystallography. The unique feature of this new radical germylzincation reaction is that the C(sp2)–Zn bond formed remains available for subsequent in situ Cu(I)- or Pd(0)-mediated C–C or C–heteroatom bond formation with retention of the double bond geometry. These protocols offer modular access to elaborated tri- and tetrasubstituted vinylgermanes decorated with heteroatom substituents β to germanium that are useful for the preparation of stereodefined alkenes.
    Mots-clés : POLE 1, ROCS.


  • S. De, L. - M. Chamoreau, H. El Said, Y. Li, A. Flambard, M. - L. Boillot, S. Tewary, G. Rajaraman, et R. Lescouëzec, « Thermally-Induced Spin Crossover and LIESST Effect in the Neutral [FeII(Mebik)2(NCX)2] Complexes: Variable-Temperature Structural, Magnetic, and Optical Studies (X = S, Se; Mebik = bis(1-methylimidazol-2-yl)ketone) », Frontiers in Chemistry, vol. 6, août 2018.


  • S. De, S. Tewary, D. Garnier, Y. Li, G. Gontard, L. Lisnard, A. Flambard, F. Breher, M. - L. Boillot, G. Rajaraman, et R. Lescouëzec, « Solution and Solid-State Study of the Spin-Crossover [FeII(R-bik)3](BF4)2 Complexes (R = Me, Et, Vinyl) », European Journal of Inorganic Chemistry, vol. 2018, nᵒ 3-4, p. 414-428, janv. 2018.
    Résumé : The magnetic properties of three spin-crossover complexes, [FeII(R-bik)3](BF4)2·nH2O (1–3), based on bis(imidazolyl)ketone ligands, were investigated in solution and the solid state. Their properties were compared with those of the ketone-free analogue, [FeII(bim)3](OTf)2 (4). The alkyl and vinyl R groups have weak influence on the tran

    sition temperature, T1/2, in solution, while stronger differences are observed in the solid state, because different intermolecular interactions occur in 1–3. The spin-state equilibria in solution were followed by SQUID magnetometry and the Evans NMR spectroscopy method. Interestingly, the equilibria can also be simply and efficiently probed by following the temperature dependence of an adequately chosen 1H chemical shift. Overall, these experiments give coherent results, with T1/2 located between 320 and 335 K, a narrow range, in comparison with the solid state. DFT calculations have allowed the rationalization of the magnetic differences. The molecular-orbital and spin-density calculations reveal that the presence of the C=O group between the imidazolyl units in the ligands of 1–3 leads to an extended aromatic system, an effective π-acceptor effect, stabilizing the LS state and reducing the LS–HS gap, in comparison with 4.
    Mots-clés : Density functional calculations, ERMMES, Iron, Paramagnetic NMR spectroscopy, POLE 2, Spin crossover.
    Pièce jointe Full Text PDF 3.1 Mo (source)


  • S. Dhifaoui, C. Mchiri, P. Quatremare, V. Marvaud, A. Bujacz, et H. Nasri, « Molecular structure, magnetic properties, cyclic voltammetry of the low-spin iron(III) Bis(4-ethylaniline) complex with the para-chloro substituted meso-tetraphenylporphyrin », Journal of Molecular Structure, vol. 1153, p. 353-359, févr. 2018.
    Résumé : In this study, the preparation of a new iron(III) hexacoordinated metalloporphyrin namely the bis(4-ethylaniline){meso-tetra(para-chlorophenyl)porphyrinato}iron(III) triflate hemi-4-ethylaniline monohydrate with the formula [FeIII(TClPP)(PhEtNH2)2]SO3CF3•1/2PhEtNH2•H2O (I) was reported. This is the first example of an iron(III) metalloporphyrin bis(primary amine) with an aryl group adjacent to the amino group. This species was characterized by elemental, spectroscopic analysis including UV–visible and IR data, cyclic voltammetry, SQUID measurements and X-ray molecular structure. The mean equatorial distance between the iron(III) and the nitrogens of the porphyrin is appropriate for a low-spin (S = 1/2) iron(III) porphyrin complex. The magnetic data confirm the low-spin state of our ferric derivative while the cyclic voltammetry indicates a shift of the half potential E1/2[Fe(III)/Fe(II)] of complex (I) toward more negative value. In the crystal of (I), the [FeIII(TClPP)(PhEtNH2)2]+ ions, the triflate counterions and the water molecules are involved in a number of O__H⋯O, N__H⋯O, C–H⋯O and C__H⋯π intermolecular interactions forming a three-dimension network.
    Mots-clés : E-POM, Iron(III) porphyrins, Magnetic data, POLE 2, UV–Visible, X-ray molecular structure.


  • S. Dhifaoui, S. Nasri, G. Gontard, A. C. Ghosh, Y. Garcia, C. Bonifàcio, S. Najmudin, V. Marvaud, et H. Nasri, « Synthesis, Mössbauer, cyclic voltammetry, magnetic properties and molecular structures of the low-spin iron(III) bis(pyrazine) complexes with the para-fluoro and para-chloro substituted meso-tetraphenylporphyrin », Inorganica Chimica Acta, vol. 477, p. 114-121, mai 2018.
    Résumé : Two new bis(pyrazine) iron(III) meso-porphyrin complexes are reported here: the bis(pyrazine)[5,10,15,20-tetra(para-fluoro-phenyl)porphyrinato]iron(III) triflate; [Fe(TFPP)(pyz)2]SO3CF3 (1) and the bis(pyrazine)[5,10,15,20-tetra(para-chlorophenyl)porphyrinato]iron(III) triflate; [Fe(TClPP)(pyz)2]SO3CF3 (2). The X-ray molecular structures of 1–2 show that the planes of the two pyrazine axial ligands are perpendicular and that the porphyrin macrocycles of these derivatives are very distorted, leading to a short average equatorial iron-pyrrole N atoms distance appropriate for low-spin ferric porphyrinates. The Mössbauer data of 1–2 feature relatively low values of the quadrupole splitting (ΔEQ ∼ 1.20 mm.s−1) appropriate for low-spin Fe(III) metalloporphyrin with perpendicular orientation of N-donor planar ligands. The temperature dependence of the magnetic susceptibility and the magnetization curves have shown that the results for complexes 1–2 confirm the low-spin state of our two-ferric species, while the cyclic voltammetry data show that the half potential [Fe(III)/Fe(II)] values are shifted anodically compared to the β-pyrrole substituted porphyrin octaethylporphyrin with parallel bis(N-donor) planar axial ligands.
    Mots-clés : E-POM, Iron(III) porphyrins, Magnetic properties, Mössbauer, POLE 2, UV-visible, X-ray molecular structure.

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