CNRS Molecular Chemistry Institute of Burgundy University

Dijon, France

CNRS Molecular Chemistry Institute of Burgundy University

Dijon, France
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Bertrand B.,University of Groningen | Bertrand B.,CNRS Molecular Chemistry Institute of Burgundy University | Casini A.,University of Groningen
Dalton Transactions | Year: 2014

From wedding rings on fingers to stained glass windows, by way of Olympic medals, gold has been highly prized for millennia. Nowadays, organometallic gold compounds occupy an important place in the field of medicinal inorganic chemistry due to their unique chemical properties with respect to gold coordination compounds. In fact, several studies have proved that they can be used to develop highly efficient metal-based drugs with possible applications in the treatment of cancer. This Perspective summarizes the results obtained for different families of bioactive organometallic gold compounds including cyclometallated gold(iii) complexes with C,N-donor ligands, gold(i) and gold(i/iii) N-heterocyclic (NHC) carbene complexes, as well as gold(i) alkynyl complexes, with promising anticancer effects. Most importantly, we will focus on recent developments in the field and discuss the potential of this class of organometallic compounds in relation to their versatile chemistry and innovative mechanisms of action. © 2014 The Royal Society of Chemistry.

Vorotyntsev M.A.,CNRS Molecular Chemistry Institute of Burgundy University | Antipov A.E.,Mendeleev University of Chemical Technology
Electrochimica Acta | Year: 2017

Theory of the steady-state electroreduction of bromate-anion at rotating disk electrode has been developed. Bulk solution contains high concentrations of bromate anion and a strong acid (which are non-electroactive at the electrode) as well as a tracer amount of bromine. The current passes owing to bromine which is reduced to bromide ion that participates further in the comproportionation reaction with bromate anion, with regeneration of bromine. This process has been described for the first time on the basis of convective diffusion transport equations for solute components, bromate and bromide ions as well as bromine, with taking into account the difference of their diffusion coefficients. Approximate analytical solutions for all concentration distributions have been derived. It has been demonstrated that the passage of the bromate process depends crucially on the value of the ratio of two characteristic lengths: individual diffusion-layer thicknesses determined for each transporting component by an interplay of the diffusion and convection mechanisms, and kinetic layer thickness where the comproportionation reaction takes place. For small values of their ratio, bromide ions cross the diffusion layer and react with bromate ions only in the bulk solution so that this process does not affect the electrode reaction and the current is very weak since it is related to reduction of bromine from the bulk solution. For moderate values of this parameter (if the ratio of these thicknesses is less than 6), a thin kinetic layer is formed deeply inside the diffusion layer where the comproportionation reaction is localized while bromide ions are absent in the outer part of the diffusion layer where bromate ions are transported from the bulk solution towards the kinetic layer and bromine is transferred in the opposite direction. Under such conditions, this bromine flux to the bulk solution makes insufficiently efficient the redox cycle formed by the electrode and comproportionation reactions, and the passing current remains relative weak. Finally, for large values of the key parameters (if the ratio of these layer thicknesses exceeds its critical value equal to 6), the redox cycle demonstrates its autocatalytic features, i.e. the reduction of bromate ions may lead to accumulation of enormous amounts of the redox couple components, bromine and bromide ion, near the electrode surface, thus resulting in a very strong current, comparable with (or even exceeding) the formally defined “diffusion-limited current for bromate anion”. Expressions for the concentration distributions inside the (thin) kinetic layer, as well as those for the maximal current density, derived within the framework of the convective-diffusion theory are in agreement with those found for the Generalized Nernst Layer model proposed by us earlier. On the contrary, there is a marked deviation of these results from those for the conventional Nernst layer model, i.e. this simplified approach is not applicable for quantitative description of the process, even though it provides its correct qualitative picture. For the outer part of the diffusional layer the newly derived concentration distributions are essentially different from predictions of both previous approaches. © 2017 Elsevier Ltd

Zinovyeva V.A.,CNRS Molecular Chemistry Institute of Burgundy University | Vorotyntsev M.A.,CNRS Molecular Chemistry Institute of Burgundy University | Bezverkhyy I.,University of Burgundy | Chaumont D.,University of Burgundy | Hierso J.-C.,CNRS Molecular Chemistry Institute of Burgundy University
Advanced Functional Materials | Year: 2011

Pd@PPy hybrid catalytic materials are synthesized in water via redox polymerization reaction of pyrrole with [Pd(NH3)4Cl 2]. The nanocomposites formed are composed of highly dispersed palladium particles which are either zerovalent or easily reducible, and are embedded in spherical polypyrrole globules. A unique combination of high palladium dispersion (NP size: 2.4 nm) and elevated palladium content (35 wt%) is obtained. The components of these novel nanocomposites are characterized by means of FTIR, XPS, XRD, SEM, and TEM microscopy techniques. The process of formation in solution is also monitored using UV-visible and DLS techniques. The application of these novel hybrid nanomaterials in the palladium-catalyzed direct arylation of heteroaromatics is reported. High efficiency in C-C bond formation is obtained using these materials. Furans and thiophenes are arylated by using bromoarenes. Pd@PPy nanocomposites can efficiently couple n-butyl furan and n-butyl thiophene with bromobenzene and bromoquinoline, as well as with activated or deactivated electron-poor and electron-rich functionalized bromoarenes. Thus, a clean reaction process is developed that combines the absence of organic ligand in catalytic reactions and easy recovery of Pd@PPy nanocomposite via simple filtration. Preliminary kinetic and post-catalysis studies suggest a molecular or colloidal soluble active species. These very active species are efficiently delivered by the nanocomposites and susceptible to a surprisingly uniform back redeposition within the polypyrrole support. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Digard E.,CNRS Molecular Chemistry Institute of Burgundy University | Andrieu J.,CNRS Molecular Chemistry Institute of Burgundy University | Cattey H.,CNRS Molecular Chemistry Institute of Burgundy University
Inorganic Chemistry Communications | Year: 2012

The preliminary studies of coordination properties of one donor stabilized-phosphenium adduct have been explored in copper chemistry. The preparation as well as the characterization of first examples of donor stabilized-phosphenium copper(I) complexes is reported in the paper. Thus, the direct addition of CuBr.SMe 2 to an equivalent amount of cationic P-ligands (L 1 + or L 2 +)(PF 6), with and, following by a crystallization in acetonitrile/Et 2O led to first copper complexes [(L 1,2 +)CuBr 2 -] 1 and 3 and [(L 1,2 +)Cu +(NCMe) 3 +](PF 6 -) 2 2 and 4 in a 1:1 ratio. However, when DMF/Et 2O mixture was used as crystallization solvent, a stable bromo-bridged copper(I) dimer 5 [(L 2 +)CuBr(DMF)] 2 was obtained. Molecular structures of mono- and di-nuclear copper complexes 1 and 5 have been confirmed by X-ray structure analysis. © 2012 Elsevier B.V.

Hierso J.-C.,CNRS Molecular Chemistry Institute of Burgundy University
Current Organic Chemistry | Year: 2011

Among the most common high-resolution nuclear magnetic resonance parameters (NMR parameters), nuclear spin-spin coupling provides decisive data for organic, organometallic, biological and coordination compounds characterization. This electron-mediated coupling characterized by J constant is very classically thought as transmitted by unambiguously covalently bonded atoms. Yet, experimental and theoretical NMR studies have highlighted since the sixties the existence of scalar J spin couplings operating via clearly nonbonded interactions, these couplings are often called "through-space" internuclear spin-spin couplings (TS couplings). We discovered that the through-space spin coupling was not only a phenomenon detectable in fluorinated constrained organic molecules, but also in organometallic and coordinating compounds, and especially in palladium and group 10 coordination complexes of constrained polyphosphine ligands. The present article aims at revealing the TS contribution of indirect nuclear spin-spin in ferrocenyl polyphosphine and their palladium coordination complexes. Theoretical and fundamental aspects are introduced in continuous relationship with experimental spectroscopic and structural data. The role of lone-pairs in nonbonded spin-spin coupling is disclosed and correlated with through-space distance dependence of J constant intensity within palladium and nickel halide complexes. Some important consequences in structural characterization of the compounds in solution are discussed. The spatial proximity of phosphorus atoms - recognized from TS spin couplings - is at the origin of new reactivity and mechanistic understanding in C-C palladium-catalyzed cross-coupling, which are quoted herein. Future trends in the modelling of this fascinating phenomenon, towards a better understanding, are briefly evoked. © 2011 Bentham Science Publishers.

Lamblin M.,University of Bordeaux Segalen | Nassar-Hardy L.,CNRS Institute of Molecular Sciences | Hierso J.-C.,CNRS Molecular Chemistry Institute of Burgundy University | Fouquet E.,CNRS Institute of Molecular Sciences | Felpin F.-X.,CNRS Institute of Molecular Sciences
Advanced Synthesis and Catalysis | Year: 2010

This review summarizes the progress made essentially these last ten years on heterogeneous palladium catalysis in pure water. The work covers four important palladium-catalyzed transformations for carbon-carbon bond formation: Suzuki, Heck, Sonogashira and Tsuji-Trost reactions. The discussion focuses on the efficiency and reusability of the heterogeneous catalysts as well as on the experimental conditions from a sustainable chemistry point of view. The review is introduced by a discussion on mechanistic aspects inherent to heterogeneous catalysis. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.

Platon M.,CNRS Molecular Chemistry Institute of Burgundy University | Amardeil R.,CNRS Molecular Chemistry Institute of Burgundy University | Djakovitch L.,CNRS Research on Catalysis and Environment in Lyon | Hierso J.-C.,CNRS Molecular Chemistry Institute of Burgundy University
Chemical Society Reviews | Year: 2012

A survey highlighting the most recent palladium catalytic systems produced and their performances for progress in direct synthesis of indole backbones by heterocarbocyclization of reactive substrates is provided. The discussion is developed in relation with the principles of sustainable chemistry concerning atom and mass economy. In this respect, the general convergent character of the syntheses is of particular interest (one-pot, domino, cascade or tandem reactions), and the substrates accessibility and reactivity, together with the final waste production, are also important. This critical review clearly indicates that the development of ligand chemistry, mainly phosphines and carbenes, in the last few decades gave a significant impetus to powerful functionalization of indoles at virtually all positions of this ubiquitous backbone (118 references). © 2012 The Royal Society of Chemistry.

Picquet M.,CNRS Molecular Chemistry Institute of Burgundy University
Platinum Metals Review | Year: 2013

The article presents the state-of-the-art in the industrial use of organometallic or coordination complexes as catalysts for the production of fine chemicals. Extensively reviewed by Johannes G. de Vries (DSM Innovative Synthesis BV, Geleen, The Netherlands) in the first chapter, palladium-catalyzed coupling reactions appear to be among the most popular reactions for the production of fine chemicals at the ton-scale. Provided inhibition and deactivation of the catalyst is avoided, catalytic C-C coupling may offer several advantages such as total cost reduction, tolerance to many functional groups and lower reaction temperatures. Asymmetric hydroformylation is a powerful tool to introduce chirality in pharmaceuticals. However, it has remained so far a purely academic domain with no industrial-scale application.

Haudecoeur R.,CNRS Molecular Chemistry Institute of Burgundy University | Stefan L.,CNRS Molecular Chemistry Institute of Burgundy University | Monchaud D.,CNRS Molecular Chemistry Institute of Burgundy University
Chemistry - A European Journal | Year: 2013

Natural G-quartets, a cyclic and coplanar array of four guanine residues held together through a Watson-Crick/Hoogsteen hydrogen-bond network, have received recently much attention due to their involvement in G-quadruplex DNA, an alternative higher-order DNA structure strongly suspected to play important roles in key cellular events. Besides this, synthetic G-quartets (SQ), which artificially mimic native G-quartets, have also been widely studied for their involvement in nanotechnological applications (i.e., nanowires, artificial ion channels, etc.). In contrast, intramolecular synthetic G-quartets (iSQ), also named template-assembled synthetic G-quartets (TASQ), have been more sparingly investigated, despite a technological potential just as interesting. Herein, we report on a particular iSQ named PNADOTASQ, which demonstrates very interesting properties in terms of DNA and RNA interaction (notably its selective recognition of quadruplexes according to a bioinspired process) and catalytic activities, through its ability to perform peroxidase-like hemin-mediated oxidations either in an autonomous fashion (i.e., as pre-catalyst for TASQzyme reactions) or in conjunction with quadruplex DNA (i.e., as enhancing agents for DNAzyme processes). These results provide a solid scientific basis for TASQ to be used as multitasking tools for bionanotechnological applications. A molecular swiss knife: Water-soluble synthetic G-quartets are valuable molecular tools that demonstrate interesting properties in terms of DNA/RNA interactions and catalytic activities (performing peroxidase-like hemin-mediated oxidations either in an autonomous fashion or in conjunction with quadruplex DNA; see figure). These results provide a solid scientific basis for synthetic G-quartets to be used as tools for bionanotechnological applications. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Filatov M.A.,CNRS Molecular Chemistry Institute of Burgundy University | Guilard R.,CNRS Molecular Chemistry Institute of Burgundy University | Harvey P.D.,CNRS Molecular Chemistry Institute of Burgundy University
Organic Letters | Year: 2010

"Chemical Equation Presented" A Suzuki reaction performed as a selective stepwise substitution of two boryl groups on a diarylporphyrin precursor is reported for straightforward construction of a porphyrin trimer, modeling photosynthetic donor-acceptor systems. © 2010 American Chemical Society.

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