Etherification of Functionalized Phenols with Chloroheteroarenes at Low Palladium Loading: Theoretical Assessment of the Role of Triphosphane Ligands in CO Reductive Elimination

The present study highlights the potential of robust tridentate ferrocenylphosphanes with controlled conformation as catalytic auxiliaries in CO bond formation reactions. Air-stable palladium triphosphane systems are efficient for selective heteroaryl ether synthesis by using as little as 0.2 mol% of catalyst. These findings represent an economically attractive and clean etherification of functionalized phenols, electron-rich, electron-poor and para-, meta- or ortho-substituted substrates, with heteroaryl chlorides, including pyridines, hydroxylated pyridine, pyrimidines and thiazole. The etherification tolerates very important functions in various positions, such as cyano, methoxy, amino, …

C-H Bond Arylation of Pyrazoles at the β-Position: General Conditions and Computational Elucidation for a High Regioselectivity

International audience; Direct arylation of most five-membered ring heterocycles are generally easily accessible and strongly favored at the α-position using classical palladium-catalysis. Conversely, regioselective functionalization of such heterocycles at the concurrent β-position remains currently very challenging. Herein, we report general conditions for regioselective direct arylation at the β-position of pyrazoles, while C-H α-position is free. By using aryl bromides as the aryl source and a judicious choice of solvent, the arylation reaction of variously N-substituted pyrazoles simply proceeds via β-C-H bond functionalization. The β-regioselectivity is promoted by a ligand-free palla…

Palladium-catalyzed formation of secondary and tertiary amines from aryl dihalides with air-stable ferrocenyl tri- and diphosphines: Synthesis and X-ray structure of efficient catalysts beyond [PdCl2(DPPF)]

Abstract Robust, air-stable tridentate and bidentate ferrocenylphosphines 1,2-bis(diphenylphosphino)-1′-(diisopropylphosphino)-4-tert-butylferrocene, L5, and 1,1′-bis(diisopropylphosphino)-3,3′-bis(tert-butyl)ferrocene, L9, combined with 1 mol% of [PdCl(η3-C3H5)]2 led to two new catalytic systems which allow the coupling of aniline derivatives with mono- and dihaloarenes to form functionalized diarylamines and triarylamines. The excellent selectivity of the reactions avoids the deleterious dehalogenation of the substrates and products. The X-ray structure characterization of the related complex [PdCl2(L9)] is reported in which ligand L9 in its meso form is significantly distorted.

Diastereoselective Synthesis of Dialkylated Bis(phosphino)ferrocenes: Their Use in Promoting Silver-Mediated Nucleophilic Fluorination of Chloroquinolines

International audience; The diastereoselective synthesis of dialkylated ferrocenyl bis(phosphane)s bearing aryl, alkyl, and hetero- or polycyclic substituents on the phosphino groups is reported, together with their characterization in the solid state by X-ray structure analysis and in solution by multinuclear NMR spectroscopy. Introduction of various alkyl groups on the ferrocene backbone, namely, tert-butyl, isopropyl, and trimethylsilyl, has a significant influence on the stereoselectivity of the ensuing lithiation/phosphination reactions. Only the introduction of the tert-butyl groups ensures both a high yield and perfect diastereoselectivity, which leads to the exclusive formation of t…

Direct arylation of heteroaromatic compounds with congested, functionalised aryl bromides at low palladium/triphosphane catalyst loading.

International audience; A new ferrocenyl triphosphane ligand associated to palladium was found to be an efficient catalyst for the direct coupling of highly congested, functionalised aryl bromides with a variety of heteroarenes. These coupling reactions can generally be performed by using a low-loading (0.1-0.5 mol%) of the catalyst. The present protocol tolerates important and useful functional groups, which allows for further elaboration into more sophisticated heterocyclic molecules. The straightforward arylation of heteroaromatic compounds with congested ortho-substituted aryl bromides may permit further convergent syntheses of diverse ligands, biologically active molecules and molecula…

Palladium-catalyzed heteroaryl thioethers synthesis overcoming palladium dithiolate resting states inertness: Practical road to sulfones and NH-sulfoximines

International audience; We provide efficient synthetic access to heteroaryl sulfones in two-steps using a simple palladium-1,1'-bis [(diphenyl)phosphanyl]ferrocene catalyst to form in high yields variously functionalized heteroaromatic thioethers. Pyridinyl-containing substrates can be subsequently selectively oxidized into sulfones and NH-sulfoximines by using very mild oxidation conditions with a high functional group tolerance. In the palladium catalyzed C-S coupling of heteroaromatic thiols, reactivity limitation is attached with electron-deficient thiols. We show that this limitation can be resolved by the successful use of 2-bromoheteroarenes in the C-S coupling. We established herein…

(2-Pyridyl)sulfonyl Groups for ortho -Directing Palladium- Catalyzed Carbon-Halogen Bond Formation at Functionalized Arenes

International audience; We describe an efficient palladium-catalyzed selective C-H ortho-monohalogenation (X=I, Br, Cl, F) of various functionalized (2-pyridyl) aryl-sulfones. ortho-, meta-and para-functionalization is tolerated at the arene group which undergoes C-H halogenation. Some modifications are also possible on the 2-(arylsulfonyl) heteroaryl directing groups. A comparison of the halogenation efficiency suggests that bromination is the practical method of choice, while chlorination and fluorination are possible but more challenging. Under forcing conditions ortho-dihalogenation can also be achieved.

Cover Feature: Palladium‐Catalyzed Electrophilic C–H‐Bond Fluorination: Mechanistic Overview and Supporting Evidence (Eur. J. Org. Chem. 2‐3/2019)

Functionalized Tri‐ and Tetraphosphine Ligands as a General Approach for Controlled Implantation of Phosphorus Donors with a High Local Density in Immobilized Molecular Catalysts

Supported phosphine ligands are auxiliaries of topical academic and industrial interest in catalysis promoted by transition metals. However, both controlled implantation and controlled conformation of ligands should be achieved to produce immobilized catalysts that are able to structurally “copy” efficient homogeneous systems. We provide herein a general synthetic strategy for assembling a new class of branched tetra- and triphosphine ligands with a unique controlled rigid conformation, and thus providing a high local density of phosphorus atoms for extended coordination to the metal center. We prepared new functionalized cyclopentadienyl (Cp) salts to design polyphosphines that were “ready…

Progress in palladium-based catalytic systems for the sustainable synthesis of annulated heterocycles: a focus on indole backbones

BIOVERT+LDJ; 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…

Phosphine Ligands Based on the Ferrocenyl Platform: Advances in Catalytic Cross-Couplings

Ferrocenyl skeletons tagged with a variety of donor atoms (metalloligands) have become popular in modern metal-catalyzed organic transformations, broadening the applications. Ferrocenylphosphines, such as 1′-bis(diphenylphosphino)ferrocene (dppf), have been widely used as metalloligands in academic and industrial research, motivating further investigation into novel ferrocenylphosphine ligands. The current review concentrated non-exhaustively on emblematic applications of different ferrocenylphosphine ligands in transition metal-catalyzed cross-coupling strategies. Initially, the stereochemical aspects of the ferrocenyl skeleton, nomenclature, and applications of chiral ferrocenyl phosphine…

Use of a bulky phosphine of weak σ-donicity with palladium as a versatile and highly-active catalytic system: allylation and arylation coupling reactions at 10−1–10−4mol% catalyst loadings of ferrocenyl bis(difurylphosphine)/Pd

Abstract Carbon–carbon(sp2–sp2 and sp1–sp2) and carbon–nitrogen (nucleophilic allylation) coupling processes are promoted by a catalytic system containing [PdCl(η3–C3H5)]2 with the new ferrocenyl bis(difurylphosphine) 1,1′-bis[di(5-methyl-2-furyl)phosphino]ferrocene, Fc[P(FuMe)2]2. Starting from aryl bromides or allylic acetates this versatile catalyst system may be used at low palladium loadings (10−1–10−4 mol%) in some Heck, Suzuki, Sonogashira and allylic amination reactions to give cross-coupled products in excellent yield. Remarkably high activity is obtained in allylic substitution reactions, providing a significant impetus for the development of bulky phosphines possessing weak σ-don…

A straightforward copper-free palladium methodology for the selective alkynylation of a wide variety of S-, O-, and N-based mono- and diheterocyclic bromides and chlorides

Abstract High-yield alkynylations are successfully achieved by a simple and widely accessible catalytic system for an unprecedented variety of heterocyclic bromides and chlorides in position -2, -3 or -5: pyridine, quinoline, thiophene, furan, thiazole, benzothiazole, pyrimidine, pyridazine, pyrazine, dioxepin halides are efficiently functionalized in short time reactions. This copper-free methodology employs 1 mol % palladium only, with inexpensive PPh3 and amine base. The ionic liquid solvent allows a straigtforward separation of products and recycling opportunity. Unsuitable substrates and secondary reactions are also reported in order to point out further progress in cross-coupling usin…

Different coordination modes of a 1,1′,2,2′-ferrocenyltetraphosphine: Bi- and tri-dentate behaviour with group 6 and 7 transition metals

The behaviour of 1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di(tert-butyl)ferrocene (1), acting as a homoannular or heteroannular ligand, has been studied. Due to the cisoid disposition of the phosphino groups of each ring, different coordination modes are observed. With group 6 metal carbonyls, M(CO)6, the tetraphosphine acts exclusively as a tridentate ligand. In contrast, the reaction with MnCp(CO)3 leads to complexes showing 1,1′ and 1,2 bidentate coordination modes. All these complexes have been characterised by 1H and 31P NMR spectroscopy. The molecular structures of the molybdenum complex [(1)Mo(CO)3] (2b) and the 1,1′ manganese complex [(1)MnCp(CO)] (3) have been established by X-ra…

"Through-space" 31P spin-spin couplings in ferrocenyl tetraphosphine coordination complexes: improvement in the determination of the distance dependence of J(P,P) constants

Abstract From the analysis of several nickel and palladium halide complexes of a constrained ferrocenyl tetraphosphine, the existence in solution phase of unique 31P–31P “through-space” nuclear spin–spin coupling constants (JPP) had been previously evidenced. Due to the blocked conformation of the species in solution, and based on the NMR spectra obtained for the complexes and their corresponding solid state X-ray structures, these JPP constants had been shown to clearly depend on the mutual spatial position of the corresponding phosphorus atoms. Herein, the quantitative correlation disclosed at that time (P⋯P distance dependence of coupling constants) is remarkably confirmed, and mathemati…

First Annelated Azaphosphole-Ferrocenes: Synthetic Pathways and Structures

The first annelated bis- and mono-3H-1,3-azaphosphole ferrocene sandwich compounds have been synthesized from aminoferrocenes, and their X-ray structures are compared to those of their selenide-protected P═Se analogues, showing net discrepancies both in metallocene backbone conformation and in fused-ring planarity.

Ortho -Functionalized Aryltetrazines by Direct Palladium-Catalyzed C−H Halogenation: Application to Fast Electrophilic Fluorination Reactions

International audience; A general catalyzed direct C-H functionalization of s-tetrazines is reported. Under mild reaction conditions, N-directed ortho-C-H activation of tetrazines allows the introduction of various functional groups, thus forming carbon-heteroatom bonds: C-X (X=I, Br, Cl) and C-O. Based on this methodology, we developed electrophilic mono- and poly-ortho-fluorination of tetrazines. Microwave irradiation was optimized to afford fluorinated s-aryltetrazines, with satisfactory selectivity, within only ten minutes. This work provides an efficient and practical entry for further accessing highly substituted tetrazine derivatives (iodo, bromo, chloro, fluoro, and acetate precurso…

Palladium-Catalyzed Direct Arylation of Heteroaromatics with Activated Aryl Chlorides Using a Sterically Relieved Ferrocenyl-Diphosphane

International audience; The palladium-catalyzed direct arylations at C3 or C4 positions of heteroaromatics are known to be more challenging than at C2 or C5 positions. Aryl chlorides are also challenging substrates for direct arylation of heteroaromatics. We observed that in the presence of a palladium-catalyst combining only 0.5 mol % of Pd(OAc)2 with the sterically relieved new ferrocenyl diphosphane Sylphos, the direct arylation at C3 or C4 of oxazoles, a benzofuran, an indole, and a pyrazole was found to proceed in moderate to high yields using a variety of electron deficient aryl chlorides. Turnover numbers up to 176 have been obtained with this catalyst. Assessment of the electron-don…

3D Ruthenium Nanoparticle Covalent Assemblies from Polymantane Ligands for Confined Catalysis

International audience; The synthesis of metal nanoparticle (NP) assemblies stabilized by functional molecules is an important research topic in nanoscience, and the ability to control interparticle distances and positions in NP assemblies is one of the major challenges in designing and understanding functional nanostructures. Here, two series of functionalized adamantanes, bis-adamantanes, and diamantanes, bearing carboxylic acid or amine functional groups, were used as building blocks to produce, via a straightforward method, networks of ruthenium NPs. Both the nature of the ligand and the Ru/ligand ratio affect the interparticle distance in the assemblies. The use of 1,3-adamantanedicarb…

Defying Stereotypes with Nanodiamonds: Stable Primary Diamondoid Phosphines

International audience; Direct unequal C-H bond difunctionalization of phosphorylated diamantane was achieved in high yield from the corresponding phosphonates. Reduction of the functionalized phosphonates provides access to novel primary and secondary alkyl/aryl diamantane phosphines. The prepared primary diamantyl phosphines are quite air stable compared to their adamantyl and especially alkyl or aryl analogues. This finding is corroborated by comparing the singly occupied molecular orbital energy levels of the corresponding phosphine radical cations obtained by density functional theory computations.

General route to dissymmetric heteroannular-functionalized ferrocenyl 1,2-diphosphines: selective synthesis and characterization of a new class of tri- and tetrasubstituted ferrocenyl compounds

Several monosubstituted-cyclopentadienyl anions (A-Li) and [1,2-bis(diphenylphosphino)-4-tert-butylcyclopentadienyl]lithium (B-Li) react with FeCl2 to afford a novel class of multidentate ferroceny...

Nanodiamond‐Palladium Core–Shell Organohybrid Synthesis: A Mild Vapor‐Phase Procedure Enabling Nanolayering Metal onto Functionalized sp 3 ‐Carbon

Gold-Catalyzed Suzuki Coupling of ortho -Substituted Hindered Aryl Substrates

International audience; A method that allows hindered ortho-substituted aryl iodides to be efficiently coupled to phenylboronic acid using a gold-catalyzed C-C bond formation is presented. The use of a molecularly-defined dinuclear gold chloride catalytic precursor that is stabilized by a new tetradentate (N,N')-diamino-(P,P')-diphosphino ferrocene hybrid ligand in a Suzuki-type reaction is described for the first time. Electron-rich isopropyl groups on phosphorus were found essen-tial for a superior activity, while the performances of a set of analogous gold dinuclear complexes that were fully characterized by multinuclear NMR spectroscopy and XRD analysis, were investigated. Therefore, ar…

Palladium-based catalytic systems for the synthesis of conjugated enynes by Sonogashira reactions and related alkynylations

Conjugated alkynes are recurring building blocks in natural products, a wide range of industrial intermediates, pharmaceuticals and agrochemicals, and molecular materials for optics and electronics. The palladium-catalyzed cross-coupling between sp(2)-hybridized carbon atoms of aryl, heteroaryl, and vinyl halides with sp-hybridized carbon atoms of terminal acetylenes is one of the most important developments in the field of alkyne chemistry over the past 50 years. The seminal work of the 1970s has initiated an intense search for more general and reliable reaction conditions. The interest in the catalytic activation of demanding substrates, the need to minimize the consumption of depletive r…

Diamondoid Nanostructures as sp 3 ‐Carbon‐Based Gas Sensors

Diamondoids, sp3 -hybridized nanometer-sized diamond-like hydrocarbons (nanodiamonds), difunctionalized with hydroxy and primary phosphine oxide groups, enable the assembly of the first sp3 -C-based chemical sensors by vapor deposition. Both pristine nanodiamonds and palladium nanolayered composites can be used to detect toxic NO2 and NH3 gases. This carbon-based gas sensor technology allows reversible NO2 detection down to 50 ppb and NH3 detection at 25-100 ppm concentration with fast response and recovery processes at 100 °C. Reversible gas adsorption and detection is compatible with 50 % humidity conditions. Semiconducting p-type sensing properties are achieved from devices based on prim…

Nanodiamonds: Emergence of Functionalized Diamondoids and Their Unique Applications

Selective Preparation of Diamondoid Phosphonates

We present an effective sequence for the preparation of phosphonic acid derivatives of the diamondoids diamantane, triamantane, [121]tetramantane, and [1(2,3)4]pentamantane. The reactions of the corresponding diamondoid hydroxy derivatives with PCl3 in sulfuric or trifluoroacetic acid give mono- as well as didichlorophosphorylated diamondoids in high preparative yields.

Ambident electrophilicity of 4‐nitrobenzochalcogenadiazoles: Kinetic studies and structure‐reactivity relationships

Kinetic and Electrochemical Studies of the Oxidative Addition of Demanding Organic Halides to Pd(0): the Efficiency of Polyphosphane Ligands in Low Palladium Loading Cross-Couplings Decrypted

International audience; Oxidative addition (OA) of organic halides to palladium(0) species is a fundamental reaction step which initiates the C–C bond formation catalytic processes typical of Pd(0)/Pd(II) chemistry. The use of structurally congested polyphosphane ligands in palladium-catalyzed C–C bond formation has generated very high turnover numbers (TONs) in topical reactions such as Heck, Suzuki, Sonogashira couplings, and direct sp2C–H functionalization. Herein, the OA of aryl bromides to Pd(0) complexes stabilized by ferrocenylpolyphosphane ligands L1 (tetraphosphane), L2 (triphosphane), and L3 (diphosphane) is considered. The investigation of kinetic constants for the addition of Ph…

The first catalytic method for Heck alkynylation of unactivated aryl bromides (copper-free Sonogashira) in an ionic liquid: 1 mol-percent palladium/triphenylphosphane/pyrrolidine in [BMIM][BF4] as a simple, inexpensive and recyclable system

Herein we report the studies of Heck alkynylation (copper-free Sonogashira) with aryl halides (I, Br, Cl) employing various metallic precursors, tertiary phosphanes and bases in [BMIM][BF4] as the solvent. As a result, we provide the first method that allows the coupling of a large array of substrates, either activated or deactivated bromides in an ionic liquid. Furthermore, the system of highest efficiency is unexpectedly the simplest and cheaper combination that employs [Pd(η3-C3H5)Cl]2/PPh3 at only a 1 mol-% loading with pyrrolidine as the base and in the absence of a copper salt. The coupling of sterically and electronically deactivated bromides bearing different functional groups to ar…

Linear Triphosphines as Ligands for Metal Complexes Immobilization in Ionic Liquids: Palladium-Catalyzed Methoxylation of Alkynes

Several novel palladium triphosphine complexes have been synthesized and tested as recyclable catalysts for the methoxylation of alkynes into acetals in ionic liquids. A complete conversion of phenylacetylene was achieved with only 0.2% of (Pd(Triphos)NCMe)((PF6)2) in a methanol/(BMIM)(BF4) mixture. We discovered that the addition of an ionic liquid to methanol allowed not only to increase the activity of the palladium catalyst but also to provide a recyclable catalyst which can be reused several times with a weaker drop of activity. To complete these catalytic studies, we describe the synthesis of the first poor -electron-donating/strong -electron-acceptor linear Triphosphine which, afte…

Gold(I) Complexes Nuclearity in Constrained Ferrocenyl Diphosphines: Dramatic Effect in Gold‐Catalyzed Enyne Cycloisomerization

International audience; Di-tert-butylated-bis(phosphino)ferrocene ligands bearing phosphino substituents R (R=phenyl, cyclohexyl, isopropyl, mesityl, or furyl) allow tuning the selective formation of Au(I) halide complexes. Thus, dinuclear linear twocoordinate, but also rare mononuclear trigonal three-coordinate and tetrahedral four-coordinate complexes were formed upon tuning of the conditions. Both Au(I) chloride and rarer Au(I) iodide complexes were synthesized, and their X-ray diffraction analysis are reported. The significance of the control of structure and nuclearity in Au(I) complexes is further illustrated herein by its strong effect on the efficiency and selectivity of gold-cataly…

ChemInform Abstract: A Versatile Palladium/Triphosphane System for Direct Arylation of Heteroarenes with Chloroarenes at Low Catalyst Loading.

The present new catalyst system can be used for the direct arylation of various heteroaromatic compounds at low palladium loadings.

Planar-Chiral 1,1 '-Diboryl Metallocenes: Diastereoselective Synthesis from Boryl Cyclopentadienides and Spin Density Analysis of a Diborylcobaltocene

International audience; The reaction of nonsubstituted alkali metal cyclopentadienides with haloboranes leads to similar to 90:10 mixtures of isomeric diene products that can be deprotonated to give simple boryl cyclopentadienides. We extended this transformation to the sterically hindered lithium tert-butylcyclopentadienide 1 using FBMe(s)2 (Mes = 2,4,6-trimethylphenyl) and ClBCy2 as electrophiles. The boryl group is selectively introduced in the remote position to minimize steric congestion. The new boryl dienes are obtained as mixtures of isomers, and subsequent deprotonation with MeLi or LiHMDS affords the lithium 1,3-disubstituted cyclopentadienides Sa,b in yields over 95%. Direct asse…

Synthesis and Catalytic Use of Polar Phosphinoferrocene Amidosulfonates Bearing Bulky Substituents at the Ferrocene Backbone

International audience; Anionic phosphinoferrocene amidosulfonates bearing sterically demanding t-butyl substituents in positions 3 and 3' of the ferrocene scaffold, viz. rac-(Et3NH)[Fe(η5-tBuC5H3PR2)(η5-tBuC5H3C(O)NHCH2SO3)] (R = phenyl and cyclohexyl) were synthesized by amidation of the corresponding phosphinocarboxylic acids, [Fe(η5-tBuC5H3PR2)(η5-tBuC5H3CO2H)]. These ditopic polar phosphinoferrocenes and their non-t-butylated analogues have been used as lig-ands to prepare zwitterionic (η3-allyl)palladium(II) complexes [Pd(η3-C3H5){Fe(η5-R'C5H3PR2)(η5-R'C5H3C(O)NHCH2SO3)}] (R' = H, tBu, R = Ph, Cy). Depending on the isolation procedure and crystallization condi-tions, some complexes we…

ChemInform Abstract: Thioetherification of Chloroheteroarenes: A Binuclear Catalyst Promotes Wide Scope and High Functional-Group Tolerance.

The nucleophilic substitution of a variety of chloro- and bromohetarenes with arylthiols is optimized to use [PdCl(allyl)]2 in combination with a ferrocenyltetraphosphane as ligand.

Enlarging the family of ferrocenylphosphine dinuclear rhodium complexes: synthesis and X-ray structure of a novel “A-frame”-type trimetallic Rh/Fe/Rh complex

Abstract The symmetrically substituted ligand 1,1 ′ -bis[di(5-methyl-2-furyl)phosphino]ferrocene ( 1 ) has been obtained from the bromophosphine BrP(Fu Me ) 2 and the dilithioferrocene/TMEDA adduct. The quantitative addition of this ferrocene derivative to the tetracarbonyl dimer [(CO) 4 Rh 2 {μ-(S t Bu) 2 }] leads, through decarbonylation, to the dinuclear rhodium complex [(CO) 2 Rh 2 {μ-(S t Bu) 2 }{μ- P , P -Fc[P(Fu Me ) 2 ] 2 }] ( 2 ) in high yield. A X-ray structure [ orthorhombic , space group P 2 1 2 1 2 1 ; a =11.2982(2) A, b =13.3165(3) A, c =27.2687(7) A] and the solution multinuclear NMR characterization are reported, which show that the rare “quasi-closed bridging” A-frame struc…

ChemInform Abstract: Progress in Palladium-Based Catalytic Systems for the Sustainable Synthesis of Annulated Heterocycles: A Focus on Indole Backbones

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…

A Versatile Palladium/Triphosphane System for Direct Arylation of Heteroarenes with Chloroarenes at Low Catalyst Loading

International audience; Put a ring on it: The use of an air-stable, robust palladium/tridentate phosphane catalyst in direct C[BOND]H and C[BOND]Cl activation reactions is reported (see scheme; DMAc=N,N-dimethylacetamide, TBAB=tetra-n-butylammonium bromide). Electron-rich, electron-poor, and polysubstituted furans (X=O), thiophenes (X=S), pyrroles (X=NR5), and thiazoles were arylated with chloroarenes in the presence of the catalyst.

“Through-space” nuclear spin–spin couplings in ferrocenyl polyphosphanes and diphosphino cavitands: A new way of gathering structural information in constrained P(III) ligands by NMR

Abstract Nuclear magnetic resonance is an invaluable technique for investigating a variety of important issues ranging from the determination of molecular structure to therapeutic medical imaging. In this respect, the indirect nuclear spin–spin coupling involving common nuclei such as 1 H, 13 C or 31 P provides, via the J constant, conclusive data for compound characterization in solution. This electron-mediated nuclear spin coupling is usually regarded as being transmitted by covalently bonded magnetic atoms. However, several experimental and theoretical studies, first focused on constrained organofluorides, and more recently devoted to phosphane ligands highlighted the existence of very i…

Synthesis and characterisation of a new class of phosphine-phosphonite ferrocenediyl dinuclear rhodium complexes

We previously reported the easy access to mixed ferrocenediyl ligands bearing phosphine and phosphonite moieties. Using this strategy, a new enantiopure phosphine-menthylphosphonite ferrocenediyl has been synthesised. This mixed ligand leads to original unsymmetrical dinuclear rhodium coordination-complexes. One example of this new class of “quasi-close bridging A frame” dinuclear rhodium complexes, fully characterised by multinuclear 1H, 13C, 31P and 103Rh NMR and optical rotation measurements, is presented. Preliminary tests have shown an activity improvement in the hydroformylation of oct-1-ene using the phosphine-menthylphosphonite ferrocenediyl auxiliary compared to known phosphine-pho…

Copper(I) Iodide Polyphosphine Adducts at Low Loading for Sonogashira Alkynylation of Demanding Halide Substrates: Ligand Exchange Study between Copper and Palladium

The prestabilization of copper iodide with a multidentate ferrocenyl phosphine ligand promotes the palladium-catalyzed cross-coupling of demanding halides with phenylacetylene in a selective way. Novel CuI-triphosphine adducts are described in the solid state and in solution. Their use allowed the introduction of the copper iodide cocatalyst in unprecedented low amounts (0.4 to 0.1 mol %) in systems also employing low amounts of “ligand-free” [PdII(η3-allyl)Cl]2 precursor (0.2 to 0.05 mol %). The scope of substrates is reported, and electronically or sterically deactivated bromides were efficiently coupled. Concerning aryl chlorides, electron-poor activated substrates were also coupled usin…

On the mechanistic behavior of highly efficient palladium-tetraphosphine catalytic systems for cross-coupling reactions: first spectroscopic and electrochemical studies of oxidative addition on Pd(0)/multidentate ferrocenylpolyphosphine complexes

Electrochemical studies carried out in conjunction with 31P NMR spectroscopy on the palladium(II)/palladium(0) halogeno complexes of the tetraphosphine 1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di...

ChemInform Abstract: Palladium-Polypyrrole Nanocomposites Pd@PPy for Direct C-H Functionalization of Pyrroles and Imidazoles with Bromoarenes.

Palladium–polypyrrole nanocomposites (Pd@PPy) with unique combination of high palladium dispersion (nanoparticle size 2.4 nm) and high palladium content (35 wt%) are efficient catalysts for the selective arylation of substituted pyrroles and imidazoles with either activated or deactivated aryl bromides. The performances of the recoverable supported palladium catalyst matches the best performances of homogeneous systems based on Pd(OAc)2 at 0.5–0.2 mol%, and largely overwhelm the classical Pd/C catalyst.

The functionalization of nanodiamonds (diamondoids) as a key parameter of their easily controlled self-assembly in micro- and nanocrystals from the vapor phase.

We detail herein readily accessible processes to control previously unobserved robust self-assemblies of nanodiamonds (diamondoids) in micro- and nanocrystals from their mild vapor deposition. The chemical functionalization of uniform and discernible nanodiamonds was found to be a key parameter, and depending on the type of functional group (hydroxy, fluorine, etc.) and its position on the diamondoid, the structure of the discrete deposits can vary dramatically. Thus, well-defined anisotropic structures such as rod, needle, triangle or truncated octahedron shapes can be obtained, and self-assembled edifices of sizes ranging from 20 nm to several hundred micrometers formed with conservation …

"Through-space" nuclear spin-spin J(PP) coupling in tetraphosphine ferrocenyl derivatives: a (31)P NMR and X-ray structure correlation study for coordination complexes.

Herein, we report on (31)P(31)P solution-phase "through-space" nuclear spin-spin coupling constants (J(PP)) from a novel family of organometallic tetraphosphine nickel and palladium complexes. These J(PP) constants were accurately determined through NMR iterative simulation based on the second-order spectra obtained for the compounds. The corresponding solid-state X-ray structures of the complexes were determined, and the "through-space" P.P distances are reported. Due to the blocked conformation of the species in solution, a qualitative and semiquantitative experimental correlation is obtained, which links the geometric parameters and the intensity of the corresponding P.P coupling constan…

Palladium‐Catalyzed C2−H Arylation of Unprotected (N−H)‐Indoles “On Water” Using Primary Diamantyl Phosphine Oxides as a Class of Primary Phosphine Oxide Ligands

Phenol Derivatives in Ruthenium-Catalyzed C-H Arylation: A General Synthetic Access to Azole-Based Congested Polyaromatics

Efficient palladium–ferrocenylphosphine catalytic systems for allylic amination of monoterpene derivatives

Ferrocenylphosphines added to [Pd(µ-Cl)(η3-C3H5)]2 dimeric precursor produce efficient catalysts to effect the allylic amination of terpenic allylacetates. Particularly convenient are tetrakis(diphenylphosphino)ferrocene and 1,1′-bis(diphenylphosphino)ferrocene, which allow the amination of allylacetates with good to excellent selectivity, and have turnover numbers as high as 80 000, for instance, for the formation of allylaniline. Herein, we report on reactions that selectively transform geranylacetate, nerylacetate, linalylacetate and perillylacetate into the corresponding allylic amines. These preparative methods give facile access to various products of great potential industrial intere…

ChemInform Abstract: Syntheses of Polyfunctionalized Resveratrol Derivatives Using Wittig and Heck Protocols.

In the modified Wittig reaction, Tms is used as a highly valuable protecting group of the phenolic functions of the starting arenes.

The Hydrogen‐Storage Challenge: Nanoparticles for Metal‐Catalyzed Ammonia Borane Dehydrogenation

International audience; Dihydrogen is one of the sustainable energy vectors envisioned for the future. However, the rapidly reversible and secure storage of large quantities of hydrogen is still a technological and scientific challenge. In this context, this review proposes a recent state-of-the-art on H 2 production capacities from the dehydrogenation reaction of ammonia borane (and selected related amine-boranes) as a safer solid-source of H 2 by hydrolysis (or solvolysis), according to the different developed nanoparticle-based catalysts. The review groups the results according to the transition metals constituting the catalyst according a special view to current cost/availability consid…

Aminomethyl-Substituted Ferrocenes and Derivatives: Straightforward Synthetic Routes, Structural Characterization, and Electrochemical Analysis

A variety of aminomethyl-substituted ferrocenes and the parent compounds (iminomethyl)ferrocenes, azaferrocenophanes, and diferrocenylamines can be selectively synthesized from reductive amination of 1,1′-diformylferrocene or formylferrocene. The optimized one- or two-step reactions have delivered 13 new compounds, isolated in 65–97% yields, which include tertiary (ferrocenylmethyl)amines and azaferrocenophanes by using NaBH(OAc)3 as a mild reducing agent and (iminomethyl)ferrocenes and secondary (ferrocenylmethyl)amines by using LiAlH4. X-ray structures of representative members of these ferrocene derivative families have evidenced the preferred conformation adopted by ferrocene backbones,…

Hexaphosphine: A Multifaceted Ligand for Transition Metal Coordination

We report the synthesis and characterization of the first ferrocenyl polyphosphane incorporating six phosphorus donor atoms. In this unique ligand, the cyclopentadienyl rings of the ferrocenyl backbone adopt a staggered position, which leads to a piano-stool arrangement for each of the two sets of three P atoms facing the same direction. As a consequence of its remarkable flexibility, this hexaphosphane displays versatile coordination behaviour towards metals, leading to unexpected structures of palladium and platinum bimetallic complexes. Analogous molybdenum and rhodium complexes are more classical.

Input of P, N-(phosphanyl, amino)-ferrocene hybrid derivatives in late transition metals catalysis

International audience; Unequally functionalized ferrocenes give access to valuable hemilabile reactivity in catalytic reaction. We address the synthesis of hybrid (P, N)-ferrocenyl compounds for which recent catalytic breakthrough applications have been reported, transversely in late transition metals chemistry. Palladium, nickel, rhodium, iridium, and emerging iron and gold catalysis are illustrated from selected examples, which include CC bond formation from cross-coupling and polymerization, allylic substitution, cyanation, hydroformylation, CH arylation and silylation and hydrogenation reactions.

Catalytic Efficiency of a New Tridentate Ferrocenyl Phosphine Auxiliary: Sonogashira Cross-Coupling Reactions of Alkynes with Aryl Bromides and Chlorides at Low Catalyst Loadings of 10-1 to 10-4 mol %.

[structure: see text] The catalytic activity in Sonogashira cross-coupling reactions of alkynes with a variety of aryl halides (including chlorides) using a multidentate ferrocenyl phosphine is presented. The novel mixed ferrocenyl aryl/alkyl triphosphine is thermally stable and insensitive to air or moisture, and its robustness allows aryl alkynylation at 10(-1) to 10(-4) mol % catalyst loadings with TONs up to 250,000. Copper-free coupling using phenylacetylene is also accessible in good yield.

Highly Dispersed Palladium-Polypyrrole Nanocomposites: In-Water Synthesis and Application for Catalytic Arylation of Heteroaromatics by Direct C-H Bond Activation

Pd@PPy hybrid catalytic materials are synthesized in water via redox polymerization reaction of pyrrole with [Pd(NH 3 ) 4 Cl 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 nanomateria…

Recyclable heterogeneous palladium catalysts in pure water: sustainable developments in Suzuki, Heck, Sonogashira and Tsuji-Trost reactions

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.

ChemInform Abstract: A Straightforward Copper-Free Palladium Methodology for the Selective Alkynylation of a Wide Variety of S-, O-, and N-Based Mono- and Diheterocyclic Bromides and Chlorides.

Abstract High-yield alkynylations are successfully achieved by a simple and widely accessible catalytic system for an unprecedented variety of heterocyclic bromides and chlorides in position -2, -3 or -5: pyridine, quinoline, thiophene, furan, thiazole, benzothiazole, pyrimidine, pyridazine, pyrazine, dioxepin halides are efficiently functionalized in short time reactions. This copper-free methodology employs 1 mol % palladium only, with inexpensive PPh3 and amine base. The ionic liquid solvent allows a straigtforward separation of products and recycling opportunity. Unsuitable substrates and secondary reactions are also reported in order to point out further progress in cross-coupling usin…

Palladium C–N bond formation catalysed by air-stable robust polydentate ferrocenylphosphines: a comparative study for the efficient and selective coupling of aniline derivatives to dichloroarene

The arylation of aniline derivatives with dichloroarenes under a low palladium content (below the currently used 5 to 10 mol%) was studied using nine different ferrocenylphosphine ligands, including the easily accessible 1,1′-bis(diphenylphosphino)ferrocene, DPPF. The electron-enriched air-stable tridentate ferrocenylpolyphosphine 1,2-bis(diphenylphosphino)-1′-(diisopropylphosphino)-4-tert-butylferrocene, L5, employed in 2 mol% in combination with 1 mol% [PdCl(η3-C3H5)]2 allows an efficient and selective coupling, while such demanding substrates currently induce chloroarene homocoupling and/or dehalogenation processes. The scope and limitation of the optimized system are explored, with a fo…

A general diastereoselective synthesis of highly functionalized ferrocenyl ambiphiles enabled on a large scale by electrochemical purification

International audience; A general synthesis of highly functionalized ferrocenes, which include (P,B)- and (N,B)-ambiphiles, has been developed at a multigram scale. Diastereoselective stepwise modification of di-tert-butylated ferrocenes included the unprecedented separation of electroactive species. Bulky alkyl groups on ferrocenes ensure planar chirality of ambiphiles and enforce closer proximity of antagonist Lewis functions.

Palladium-Catalysed CH Bond Electrophilic Fluorination of Highly Substituted Arylpyrazoles: Experimental and DFT Mechanistic Insights

A general protocol for palladium-catalysed CH mono- and di-fluorination of highly substituted arylpyrazoles is reported. Coupling pathways and substrate limitations are discussed in the light of complementary mechanistic experimental and density functional theory (DFT) studies. The mono- and di-ortho-fluorination of arylpyrazoles having substituted pyrazole groups and ortho-, meta-, or para-substituted arene moieties is achieved. Various pyrazole groups can efficiently promote the direct CH activation/fluorination of substrates bearing valuable reactive ester, cyano, halide and nitro functions. The presence of methoxy, methyl and trifluoromethyl is tolerated on the pyrazole directing groups…

Performances of symmetrical achiral ferrocenylphosphine ligands in palladium-catalyzed cross-coupling reactions: A review of syntheses, catalytic applications and structural properties

Abstract Ferrocene derivatives bearing donor atoms led to the generation of several classes of metallo-ligands, which collectively show an impressive diversity of applications, especially in metal-catalyzed modern organic reactions. Based on the impetus provided by the use of the diphosphine 1,1′-bis(diphenylphosphino)ferrocene (dppf) the investigations directed towards the synthesis of new ferrocenylphosphines remain of fundamental and industrial interest. The present review aims to describe the performances in palladium-catalyzed cross-coupling reactions of symmetrical achiral ferrocenylphosphine ligands, mainly diphosphines. We specifically choose to restrict our review efforts to these …

Structural diversity in coordination chemistry of tridentate and tetradentate polyphosphines of Group 6 to 10 transition metal complexes

Abstract Tridentate and tetradentate polyphosphines offer a huge variety of coordination modes to transition metals which lead, depending on the metal, to very different structural features in the resulting complexes. Steric effects being crucial in metal–phosphine complexes reactivity, a good knowledge of the molecular structures of the species is required both in the solid state and in solution. This article reviews from a structural point of view the monometallic and symmetrical homobimetallic complexes of the transition elements of Group 6 to 10 with tridentate and tetradentate phosphines. Concerning the classical triphosphines and tetraphosphines, emphasis was put on advances reported …

Nonbonded Indirect Nuclear Spin–Spin Couplings (J Couplings “Through-Space”) for Structural Determination in Small Organic and Organometallic Species

Abstract Spin–spin coupling constant J provides decisive data for organic compound characterization. This electron-mediated coupling is usually taught as transmitted between covalently bonded magnetic atoms. However, this physical interaction between nuclear spins is much more complex than that with regard to chemical bonding concept. Independent experimental and theoretical studies related to small organic and organometallic species (molecular mass below 2000 g mol − 1 ) have highlighted the existence of J couplings operating via clearly nonbonded interactions and known as “through-space” couplings. Interactions of this type are frequently reported and couplings involving 19  F, 13 C, 77 S…

ChemInform Abstract: Donor-Stabilized Phosphenium Adducts as New Efficient and Immobilizing Ligands in Palladium-Catalyzed Alkynylation and Platinum-Catalyzed Hydrogenation in Ionic Liquids.

The straightforward synthesis of a new donor-stabilized phosphenium ligand 3d by addition of bromodifurylphosphine to 1,3-dimethylimidazolium-2-carboxylate 1 is described. The obtained ligand exhibits a very strong π-acceptor character, comparable to that of triphenyl phosphite [P(OPh) 3 ] or of tris-halogenophosphines, with a v CO (A 1 ) at 2087 cm ―1 for its nickel tricarbonyl complex. This ligand, as well as the related 3a which was obtained from chlorodiphenylphosphine, were tested in palladium-catalyzed aryl alkynylation and in the platinum-catalyzed selective hydrogenation of chloronitrobenzenes, both in an ionic liquid phase. In C―C bond cross-coupling we observed that the increase o…

Conformational Control of Metallocene Backbone by Cyclopentadienyl Ring Substitution: a New Concept in Polyphosphane Ligands Evidenced by “Through-Space” Nuclear Spin-Spin Coupling. Application in heteroaromatics arylation by direct C–H activation

The present study deals with the conformational control of the metallocene backbone within ferrocenyl polyphosphane ligands and their performance in the highly topical palladium-catalyzed heteroaromatics arylation by direct C−H activation. New substituted cyclopentadienyl rings were synthesized, which allowed the assembling of original tri- and diphosphanes. The bulky cyclopentadienyl lithium salts diphenylphosphino-3-(triphenyl)methylcyclopentadienyllithium (4) and 1,2-bis(diphenylphosphino)-4-(triphenyl)methylcyclopentadienyllithium (5) were prepared in excellent yield. The assembling of these new hindered cyclopentadienyl salts (Cp) with other Cp fragments was performed in order to prepa…

Direct arylation of heterocycles: the performances of ferrocene-based polyphosphane ligands in palladium-catalyzed C-H bond activation

International audience; The palladium-catalyzed direct arylation of alkylated- furan, thiophene, and thiazole and benzoxazole heterocycles with electronically and sterically deactivated bromoarenes was selectively and efficiently promoted by ferrocenyl polyphosphanes. In this C[BOND]H bond activation reaction of heteroaromatics, the performances of polydentate di-, tri-, and tetraphosphane ligands were compared, showing that the triphosphane 1,1′,2-tris(diphenylphosphino)-4-tert-butylferrocene 3 was the most effective for the coupling. The introduction of more electron-donating (iPr) or electron-withdrawing (furyl) groups on the phosphorus atoms did not improve the ligand performances. The …

Synthesis and structural characterisation of bulky heptaaromatic (hetero)aryl o-substituted s-aryltetrazines

An expedient two-step synthesis produces in good yield polyaromatic heptacyclic (hetero)arylated o-substituted s-aryltetrazines (s-Tz) directly from diphenyl s-tetrazine. This methodology overcomes the steric limitations of classical Pinner-like syntheses encountered for o-functionalized s-Tz. A single step palladium-catalyzed N-directed C–H bond tetrahalogenation is followed by a Pd-catalyzed Suzuki (hetero)arylation that is achieved simultaneously on four sites. The single crystal X-ray diffraction structure of the resulting typical polyaromatic heptacyclic aromatic compound 3,6-bis(2,6-diphenyl)-1,2,4,5-tetrazine (3) is analyzed, together with R-functionalized peripheral phenyl derivativ…

A sterically congested 1,2-diphosphino-1'-boryl-ferrocene: synthesis, characterization and coordination to platinum.

International audience; A new class of tritopic ferrocene-based ambiphilic compound has been prepared by assembling diphosphino- and boryl-substituted cyclopentadienides at iron. The presence of five sterically demanding substituents on the ferrocene platform induces conformation constraints, as apparent from XRD and NMR data, but does not prevent chelating coordination to platinum. The Lewis acid moiety is pendant in both the free ligand and the platinum complex.

ChemInform Abstract: Recyclable Heterogeneous Palladium Catalysts in Pure Water: Sustainable Developments in Suzuki, Heck, Sonogashira and Tsuji-Trost Reactions

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.

Nanocatalysts for High Selectivity Enyne Cyclization: Oxidative Surface Reorganization of Gold Sub-2-nm Nanoparticle Networks

International audience; Ultrasmall gold nanoparticles (NPs) stabilized in networks by polymantane ligands (diamondoids) were successfully used as precatalysts for highly selective heterogeneous gold-catalyzed dimethyl allyl(propargyl)malonate cyclization to 5-membered conjugated diene. Such reaction usually suffers from selectivity issues with homogeneous catalysts. This control over selectivity further opened the way to one-pot cascade reaction, as illustrated by the 1,6-enyne cycloisomerization–Diels–Alder reaction of dimethyl allyl propargyl malonate with maleic anhydride. The ability to assemble nanoparticles with controllable sizes and shapes within networks concerns research in sensor…

Syntheses of polyfunctionalized resveratrol derivatives using Wittig and Heck protocols

Improved protocols for Wittig reaction and palladium-catalyzed Heck coupling give expedient access to a series of unprecedented polyfunctionalized artificial-resveratrol derivatives. In the modified Wittig protocol, trimethylsilyl was used as a highly valuable protective group of the phenolic functions of starting aromatic materials. A clean O-alkylation of hydroxylated stilbenes with ethylene carbonate was also conducted. Thus, Wittig reaction followed by hydroxyethylation take place one-pot with only carbon dioxide as waste. Additionally, a palladium-catalyzed Heck coupling strategy was developed by using ferrocenyl phosphane ligands, and multi-functionalized hydroxylated stilbenes were o…

Diphosphines of dppf-Type Incorporating Electron-Withdrawing Furyl Moieties Substantially Improve the Palladium-Catalysed Amination of Allyl Acetates

Highly active Pd/diphosphine catalytic systems incorporating new, air-stable ferrocenyl-furylphosphines allow nucleophilic allylic amination at room temperature with unprecedented turnover frequencies. For instance, in the presence of 0.01 mol % catalyst the coupling of aniline to allyl acetate occurs at a TOF of more than 10,000 h - 1 ; even the addition of the less nucleophile morpholine to allyl acetate is observed with a TOF of 4250 h - 1 . The amination of the sterically demanding geranyl acetate, a monoterpene derivative of interest in the flavour industry, at low catalyst loadings demonstrates the scope of this methodology, which provides in addition noticeable advantages in terms of…

Ultra-Low Catalyst Loading as a Concept in Economical and Sustainable Modern Chemistry: The Contribution of Ferrocenylpolyphosphane Ligands

The challenge of sustainability in modern chemistry will be met with new technologies and processes provided significant progress is made in several key research areas, such as the expansion of chemistry from renewable feedstock, the design of environmentally benign chemicals and solvents, the minimization of depletive resources, and the development of high-performance catalysis. In this prospect, ligand chemistry is a pivotal science that links modern-organic,-inorganic, -organometallic, and -coordination chemistry through a vast number of valuable applications, precisely associated to catalysis. We review in this article our recent work on catalysis promoted by original ferrocenyl tetra-,…

Palladium-Katalysatorsysteme für die Synthese von konjugierten Eninen durch Sonogashira-Kupplungen und verwandte Alkinylierungen

Konjugierte Alkine sind stets wiederkehrende Synthesebausteine in Naturstoffen, zahlreichen unverzichtbaren industriellen Zwischenstufen, in Pharmazeutika und Agrochemikalien sowie in molekularen Materialien fur Optik und Elektronik. Daher zahlt die palladiumkatalysierte Verknupfung der sp2-hybridisierten Kohlenstoffatome von Aryl-, Heteroaryl- und Vinylhalogeniden mit den sp-hybridisierten Kohlenstoffatomen von terminalen Acetylenen in einer Kreuzkupplung unbestreitbar zu den bedeutendsten Entwicklungen der Alkinchemie in den vergangenen funfzig Jahren. Auf die grundlegenden Arbeiten der 1970er folgte eine intensive Suche nach allgemeineren und verlasslicheren Reaktionsbedingungen. Das Int…

Diamondoids: functionalization and subsequent applications of perfectly defined molecular cage hydrocarbons

The term “diamondoid” describes cage hydrocarbon molecules that are superimposable on the diamond lattice. Diamondoids that are formally built by face-fusing of adamantane units, namely diamantane, triamantane, tetramantane, etc., have fascinated chemists since the beginning of the last century. The functionalization of these perfectly defined (C,H)-molecules is described here. Thus, diamondoid halides and diamondoid alcohols are first rank precursors for amino and phosphine-substituted diamondoids that have proved to be highly useful in therapeutic applications and metal catalysis, respectively. The extent of functionalization and polyfunctionalization achieved for adamantane and diamantan…

Gold(I) Complexes of Ferrocenyl Polyphosphines: Aurophilic Gold Chloride Formation and Phosphine-Concerted Shuttling of a Dinuclear [ClAu···AuCl] Fragment

International audience; A smart steric control of the metallocene backbone in bis- and poly(phosphino)ferrocene ligands favors intramolecular aurophilic interactions between [AuCl] fragments in polynuclear gold(I) complexes. We synthesized and characterized by multinuclear NMR and X-ray diffraction analysis mono-, di-, and polynuclear gold complexes of constrained ferrocenyl diphosphines, which bear either bulky tert-butyl groups or more flexible siloxane substituents at the cyclopentadienyl rings. The complexes meso-1,1'-bis-(diphenylphosphino)-3,3'-di-tert-butylferrocene (4-m), rac-1,1'-bis[bis-(5-methy1-2-furyl)phosphino]-3,3'-di-tert-butyfferrocene (5-r), and rac-1,1'-bis ( diphenylphos…

Ultra‐Low Catalyst Loading as a Concept in Economical and Sustainable Modern Chemistry: The Contribution of Ferrocenylpolyphosphane Ligands (Eur. J. Inorg. Chem. 24/2007)

The cover picture shows an X-ray illustration of the multidentate ferrocenylpolyphosphane 1,1′,2,2′-tetrakis(diphenylphosphanyl)-4,4′-di-tert-butylferrocene. The cisoid conformation of the molecule, evidenced at the solid state, is conserved in solution; the phosphorus arrangement led to a rarely demonstrated multiple-coordination behaviour towards palladium, possibly useful in ultra-low catalyst loading reactions due to an improved stabilization of the metal atom. The multiple phosphane arms and their orientation resemble the elegant and intelligent creature that is the Giant Pacific Octopus (specimen from the Alaska SeaLife Centre in Seward, photo published with the kind permission of Mol…

Unsymmetrically Substituted Bis(phosphino)Ferrocenes Triggering Through-Space 31(P, P′)-Nuclear Spin Couplings and Encapsulating Coinage Metal Cations

International audience; We describe unsymmetrically substituted di-tert-butylated 1,1'-bis(phosphino)ferrocenes, with phosphino substituents R = [5-methyl]-2-furyl = Fu, and R' = phenyl (4a), i-propyl (4b). A modular synthetic approach was applied from the di-tert-butylated ferrocene platform (1), which lead to the formation of new diphosphines by using 1,1'bis(diiodo)-3,3'-bis(tert-butyl)ferrocene (2) as synthetic precursor. In contrast to the cousin non-alkylated unsymmetrically substituted diphosphino-ferrocenes which were reported up to now, these diphosphines showed strong (31 P, P')nonbonded (" ug-p e") nuclear spin-spin coupling. The strength of such internuclear spin-spin coupling c…

Coordination Chemistry of a Bis(Tetrazine) Tweezer: A Case of Host-Guest Behavior with Silver Salts

The carbon-carbon cross-coupling of phenyl s-tetrazine (Tz) units at their ortho-phenyl positions allows the formation of constrained bis(tetrazines) with original tweezer structures. In these compounds, the face-to-face positioning of the central tetrazine cores is reinforced by π-stacking of the electron-poor nitrogen-containing heteroaromatic moieties. The resulting tetra-aromatic structure can be used as a weak coordinating ligand with cationic silver. This coordination generates a set of bis(tetrazine)-silver(I) coordination complexes tolerating a large variety of counter anions of various geometries, namely, PF6−, BF4−, SbF6−, ClO4−, NTf2−, and OTf−. These compounds were characterized…

Modular functionalized polyphosphines for supported materials: previously unobserved (31)P-NMR «through-space» ABCD spin systems and heterogeneous palladium-catalysed C-C and C-H arylation.

The modular design of polyphosphines, diversely functionalized for facile immobilization on virtually any kind of support, is reported. Previously unobserved ABCD (31)P NMR spin-spin systems evidence the control exercised on the polyphosphines conformation. We illustrate the catalytic performance at low Pd loading of the recyclable immobilized polyphosphines in C-C bond formation reactions.

Selective formation of a unique diphosphonium-diphosphine from a tetraphosphine double protonation induced by zirconium salts

A mixed ferrocenyl diphosphonium-diphosphine cation, associated with two [ZrCl(5).thf](-) anions, is obtained from a ferrocenyl tetraphosphine, as a unique didentate ionic metalloligand in a perfectly selective reaction induced by ZrCl(4) in THF.

ChemInform Abstract: ortho-Functionalized Aryltetrazines by Direct Palladium-Catalyzed C-H Halogenation: Application to Fast Electrophilic Fluorination Reactions.

A general catalyzed direct C-H functionalization of s-tetrazines is reported. Under mild reaction conditions, N-directed ortho-C-H activation of tetrazines allows the introduction of various functional groups, thus forming carbon-heteroatom bonds: C-X (X=I, Br, Cl) and C-O. Based on this methodology, we developed electrophilic mono- and poly-ortho-fluorination of tetrazines. Microwave irradiation was optimized to afford fluorinated s-aryltetrazines, with satisfactory selectivity, within only ten minutes. This work provides an efficient and practical entry for further accessing highly substituted tetrazine derivatives (iodo, bromo, chloro, fluoro, and acetate precursors). It gives access to …

(Cycloheptadienyl)diphenylphosphine: A Versatile Hybrid Ligand

(3,5-Cycloheptadienyl)diphenylphosphine is easily synthesized from the reaction of diphenylphosphine with 1,3,5-cycloheptatriene. This new phosphine-diene has been coordinated as a monodentate P ligand with Pt, Pd, Au, Ni, and Ru; as a bidentate (P, olefin) ligand with Pt and Pd; and as a tridentate (P, diene) ligand with Rh. Fluxional properties of several complexes have been studied via NMR experiments and theoretical consideration.

1,1prime-Binaphthyl-2-methylpyridinium-based peroxophosphotungstate salts: synthesis, characterization, and their use as oxidation catalysts

A series of 1,1′-binaphthyl-2-methylammonium and pyridinium salts 6, 7, and 8 was synthesized through the coupling reaction of 2-(bromomethyl)-1,1′-binaphthalene (5) with the dendritic tetraallyl pyridinedicarbinol dendron 2 as well as triethylamine and 4-tert-butylpyridine. Tetraallyl pyridinedicarbinol dendron 2 was prepared by allylation of commercially available diethyl pyridine-3,5-dicarboxylate (1). The allylation of 2 with allyltrimethylsilane in the presence of boron trifluoride was unsuccessful, as tetraallyl pyridinedicarbinol trifluoroboron adduct 3 was obtained instead of expected hexaallylpyridine compound 4. The catalytic hydrogenation of allyl groups of the ammonium salt of 2…

{1,1′-Bis[bis(5-methyl-2-furyl)phosphino]ferrocene-κ2P,P′}dichloroplatinum(II) dichloromethane hemisolvate

The synthesis of the title compound, [FePtCl2(C15H14O2P)2]·0.5CH2Cl2, has been achieved by reacting PtCl2(PhCN)2 with the 1,1′-bis­[bis­(5-methyl-2-furyl)phosphino]ferrocene chelating ligand. The environment at the Pt atom can be described as distorted square-planar, with two cis-Cl atoms and two cis-P atoms.

ChemInform Abstract: “Through-Space” Nuclear Spin-Spin Couplings in Ferrocenyl Polyphosphanes and Diphosphino Cavitands: A New Way of Gathering Structural Information in Constrained P(III) Ligands by NMR

Abstract Nuclear magnetic resonance is an invaluable technique for investigating a variety of important issues ranging from the determination of molecular structure to therapeutic medical imaging. In this respect, the indirect nuclear spin–spin coupling involving common nuclei such as 1 H, 13 C or 31 P provides, via the J constant, conclusive data for compound characterization in solution. This electron-mediated nuclear spin coupling is usually regarded as being transmitted by covalently bonded magnetic atoms. However, several experimental and theoretical studies, first focused on constrained organofluorides, and more recently devoted to phosphane ligands highlighted the existence of very i…

Electrosynthesis as a powerful method for the generation of catalytic intermediates: efficient isolation of a palladium aryl halide oxidative addition product.

International audience; Polyphosphane ligands of controlled conformation promote highly efficient palladium-catalyzed cross-coupling reactions. Electrosynthesis has been used as a new straightforward method to obtain important intermediates in the search for a better mechanistic understanding. As a proof of concept, the facile synthesis of a phenyl iodopalladium(II) complex (2) was conducted at the electrolysis scale from a readily electrogenerated unstable Pd0 precursor.

Porous Materials Based on 3-Dimensional Td-Directing Functionalized Adamantane Scaffolds and Applied as Recyclable Catalysts

Porous materials have been of high scientific and technological interest owing to their unique performances in many topical applications related to multiphasic functional systems: gas separation and storage, heterogeneous catalysis, energy conversion, etc. We review herein the synthetic strategies applied for using functionalized adamantane derivatives as polyhedral (mainly tetrahedral, Td-directing) building units of three-dimensional (3-D) porous supramolecular structures and nanomaterials, either purely organic or within metal hybrid frameworks. The resulting materials are currently used in varied heterogeneous (or supported) transition metal catalysis and organocatalysis, including rece…

New concepts in multidentate ligand chemistry: effects of multidentarity on catalytic and spectroscopic properties of ferrocenyl polyphosphines.

This tutorial review devoted to ligand chemistry deals with the design and properties of ferrocenyl polyphosphines, an original class of multidentate ligands. The development of a varied library of ferrocenyl tetra-, tri- and diphosphine ligands is reviewed. The multidentate nature of these species has led to unique spectroscopic and catalytic properties, in which the spatial proximity of phosphorus atoms is crucial. Regarding their catalytic applications, the key issues of catalyst longevity and ultralow catalyst loadings are discussed. Another part is concerned with fundamental advances gained in physical chemistry for structure elucidation by the study of the intriguing “through-space” N…

Palladium‐Catalyzed Electrophilic C–H‐Bond Fluorination: Mechanistic Overview and Supporting Evidence

International audience; Palladium-catalyzed electrophilic fluorination is a particularly attractive and challenging synthetic issue. Because of the rapid evolution of this topic, a critical point on the mechanistic and experimental advances is provided herein. In the present review, we focused on current mechanistic understanding in electrophilic fluorination (and related halogenations) catalyzed by palladium, mainly with N-directing group. Our discussion is based on the well-characterized or calculated pertinent metal species and intermediates used for analyzing the plausible catalytic cycles. A particular effort has been devoted to gathering supporting data for the putative species involv…

Thioetherification of Chloroheteroarenes: A Binuclear Catalyst Promotes Wide Scope and High Functional-Group Tolerance

A constrained binuclear palladium catalyst system affords selective thioetherification of a wide range of functionalized arenethiols with chloroheteroaromatic partners with the highest turnover numbers (TONs) reported to date and tolerates a large variety of reactive functions. The scope of this system includes the coupling of thiophenols with six- and five-membered 2-chloroheteroarenes (i.e., functionalized pyridine, pyrazine, quinoline, pyrimidine, furane, and thiazole) and 3-bromoheteroarenes (i.e., pyridine and furane). Electron-rich congested thiophenols and fluorinated thiophenols are also suitable partners. The coupling of unprotected amino-2-chloropyridines with thiophenol and the s…

C–H Halogenation of Pyridyl Sulfides Avoiding the Sulfur Oxidation: A Direct Catalytic Access to Sulfanyl Polyhalides and Polyaromatics

Palladium-catalyzed oxidative C–H halogenation and acetoxylation reactions of S-unprotected sulfides, selectively directed by pyridinyl groups, allows the formation of C–X bonds (X = I, Br, Cl, OAc) by using simple halosuccinimide or phenyliodine diacetate (PIDA) oxidants. The undesired formation of sulfoxides and/or sulfones, which are usually observed under oxidative conditions, is fully obviated. Under the solvent-dependent conditions that we proposed, sulfide C–H functionalization is achieved in less than 1 h without any direct electrophilic halogenation at the pyridine moiety. N-Directed ortho-C–H activation of aryl also facilitates dibromination reactions which are hardly accessible w…

Donor-Stabilized Phosphenium Adducts as New Efficient and Immobilizing Ligands in Palladium-Catalyzed Alkynylation and Platinum-Catalyzed Hydrogenation in Ionic Liquids

The straightforward synthesis of a new donor-stabilized phosphenium ligand 3d by addition of bromodifurylphosphine to 1,3-dimethylimidazolium-2-carboxylate 1 is described. The obtained ligand exhibits a very strong π-acceptor character, comparable to that of triphenyl phosphite [P(OPh) 3 ] or of tris-halogenophosphines, with a v CO (A 1 ) at 2087 cm ―1 for its nickel tricarbonyl complex. This ligand, as well as the related 3a which was obtained from chlorodiphenylphosphine, were tested in palladium-catalyzed aryl alkynylation and in the platinum-catalyzed selective hydrogenation of chloronitrobenzenes, both in an ionic liquid phase. In C―C bond cross-coupling we observed that the increase o…

ChemInform Abstract: New Concepts in Multidentate Ligand Chemistry: Effects of Multidentarity on Catalytic and Spectroscopic Properties of Ferrocenyl Polyphosphines

This tutorial review devoted to ligand chemistry deals with the design and properties of ferrocenyl polyphosphines, an original class of multidentate ligands. The development of a varied library of ferrocenyl tetra-, tri- and diphosphine ligands is reviewed. The multidentate nature of these species has led to unique spectroscopic and catalytic properties, in which the spatial proximity of phosphorus atoms is crucial. Regarding their catalytic applications, the key issues of catalyst longevity and ultralow catalyst loadings are discussed. Another part is concerned with fundamental advances gained in physical chemistry for structure elucidation by the study of the intriguing “through-space” N…

Palladium–Polypyrrole Nanocomposites Pd@PPy for Direct C–H Functionalization of Pyrroles and Imidazoles with Bromoarenes

International audience; Palladium–polypyrrole nanocomposites (Pd@PPy) with unique combination of high palladium dispersion (nanoparticle size 2.4 nm) and high palladium content (35 wt%) are efficient catalysts for the selective arylation of substituted pyrroles and imidazoles with either activated or deactivated aryl bromides. The performances of the recoverable supported palladium catalyst matches the best performances of homogeneous systems based on Pd(OAc)2 at 0.5–0.2 mol%, and largely overwhelm the classical Pd/C catalyst.

Ferrocenyl (P,N)-diphosphines incorporating pyrrolyl, imidazolyl or benzazaphospholyl moieties: Synthesis, coordination to group 10 metals and performances in palladium-catalyzed arylation reactions

Abstract Three novel symmetrical ferrocenyl diphosphines with tertiary phosphorus atoms holding respectively nitrogen-containing heterocyclic derivatives of pyrrole, imidazole and benzazaphosphole were synthesized and characterized. Up to now, integration of heteroaromatic fragments, or more generally hetero-cycles, as substituents on the tertiary phosphines of symmetrical ferrocenyl diphosphines has been limited to the furyl motif. Their coordination to palladium and platinum group 10 transition metals was exemplified, and analyzed using single crystal X-ray diffraction. The performances obtained in palladium-catalyzed copper-free Sonogashira and Suzuki cross-coupling reactions using bromo…

Vers une catalyse durable, économe d'atomes et éco-responsable : 0,0001 % de métal, une dose presque homéopathique pour la synthèse pharmaceutique et agrochimique

International audience; Comment mettre la chimie en accord avec un développement sociétal durable, harmonieux et respectueux de l'environnement ? Des chimistes de l'Université de Bourgogne cherchent et trouvent des solutions !

Phosphorus‐Directed Rhodium‐Catalyzed C−H Arylation of 1‐Pyrenylphosphines Selective at the K ‐Region

Converging and Diverging Synthetic Strategies to Tetradentate (N,N′)-Diaminomethyl,(P,P′)-Ferrocenyl Ligands: Influence of tert-Butyl Groups on Ferrocene Backbone Conformation

Hexasubstituted hybrid tetradentate (N,N′,P,P′)-ferrocenes bearing phosphino and aminomethyl groups, plus hindering tert-butyl moieties, were synthesized by using two different strategies: a “diverging” synthesis involving successive functionalization of preformed di-tert-butylated ferrocene and a “converging” assembly of the species from appropriately substituted cyclopentadienyl rings. While the new cyclopentadienyl salts formed are of interest, their assembly with iron dichloride used as a “converging” way to produce tetradentate ferrocene ligands presented several drawbacks. Conversely, the synthesis of new tert-butylated (aminomethyl)ferrocene derivatives was found convenient to furthe…

Bridge-Clamp Bis(tetrazine)s with [N] 8 π-Stacking Interactions and Azido- s -Aryl Tetrazines: Two Classes of Doubly Clickable Tetrazines

Click chemistry at a tetrazine core is useful for bioorthogonal labeling and crosslinking. Introduced here are two new classes of doubly clickable s-aryl tetrazines synthesized by Cu-catalyzed cross-coupling. Homocoupling of o-brominated s-aryl tetrazines leads to bis(tetrazine)s structurally characterized by tetrazine cores arranged face-to-face. [N]8 π-stacking interactions are essential to the conformation. Upon inverse electron demand Diels-Alder (iEDDA) cycloaddition, the bis(tetrazine)s produce a unique staple structure. The o-azidation of s-aryl tetrazines introduces a second proximal intermolecular clickable function that leads to double click chemistry opportunities. The stepwise i…

Solvent-free ruthenium-catalysed triflate coupling as a convenient method for selective azole-o-C-H monoarylation.

Metal-catalysed ortho-directed C–H functionalization usually faces selectivity issues in the competition between mono- and disubstitution processes. We report herein the ruthenium-catalysed N-directed C–H monoarylation of arylpyrazoles with a selectivity of up to 96% or that generally reaches values above 80%. This selectivity is an effect of solvent-free conditions associated with sulfonate reagents, in the absence of frequently used acidic additives.

First copper(I) ferrocenyltetraphosphine complexes: possible involvement in Sonogashira cross-coupling reaction ?

Preparation and characterization of the first examples of copper(I) ferrocenylpolyphosphine complexes are reported. The molecular structure of complex {P,P′,P′′-[1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di-tert-butylferrocene]iodocopper(I)} (1) was solved by X-ray diffraction studies, and its fluxional behavior in solution was investigated by VT-31P NMR; both revealed a net triligated coordination preference of the ferrocenyl tetraphosphine Fc(P)4tBu with copper. The tetradentate ligand is an active auxiliary in Sonogashira alkynylation; therefore the general question of copper as a competitive coordination partner in the Pd/Cu-catalyzed Sonogashira reaction was raised and discussed. Elec…

Uncommon perspectives in palladium- and copper-catalysed arylation and heteroarylation of terminal alkynes following Heck or Sonogashira protocols: Interactions copper/ligand, formation of diynes, reaction and processes in ionic liquids

Abstract Conjugated alkynes are recurring building blocks in natural products and in a wide range of important compounds, such as pharmaceuticals, agrochemicals, or molecular materials. The palladium-catalysed cross-coupling reaction between the sp 2 -hybridized carbon atoms of aryl, heteroaryl, and vinyl halides with the sp -hybridized carbon atoms of terminal alkynes is one of the most important developments in the field of alkyne chemistry over the past 50 years. Room for improvement still exists in these important reactions of direct arylation of terminal alkynes. In this prospect, the present authors have developed several strategies aiming at improving the reactivity, the selectivity,…

Cluster Preface: Heterogeneous Catalysis

International audience; Jean-Cyrille Hierso is full professor of Chemistry since 2009, heading the group of ‘Organometallic Chemistry and Catalysis’ at the Institute of Molecular Chemistry at the University of Bourgogne Franche-Comté (UBFC). He has interest in the fields of organometallic chemistry, ligand design, homo- and heterogeneous catalysis, chemical physics, and material sciences. In 2011 he was awarded the National Prize for Coordination Chemistry from the French Chemical Society (SCF), and at the end of 2012 he was elected a junior Member of the French Professors Academy ‘Institut Universitaire de France’ (IUF).Yasuhiro Uozumi is a full professor at the Institute for Molecular Sci…

Highly Functionalized Brønsted Acidic/Lewis Basic Hybrid Ferrocene Ligands: Synthesis and Coordination Chemistry

International audience; A general challenging issue in the synthesis of hemilabile ferrocene ligands is the access to highly functionalized ferrocene starting materials. These can bear donor/acceptor atoms, additional functional and structuring spectator substituents, but the preparation of such species poses general synthetic difficulties. We report herein alternative synthetic routes to hybrid ferrocene donors such as tert-butylated phosphanylcarboxylic acids and their corresponding aldehydes. These hybrid ambiphilic species that combine Brønsted-acidic and Lewis-basic functional moieties in their structure were characterized by multinuclear NMR and single-crystal X-ray diffraction analys…

Palladium coupling catalysts for pharmaceutical applications

International audience; This review discusses recent advances made in the area of palladium-catalyzed coupling reactions and describes a selection of the catalytic systems that are useful in the preparation of valuable compounds for the pharmaceutical industry. Most of these types of syntheses have used either simple palladium salts or palladium precursors associated with electron-rich mono- or bidentate phosphine ligands as catalysts. For some reactions, ligands such as triphenyl phosphine, 1,1'-bis(diphenylphosphino)ferrocene, a carbene or a bipyridine have also been employed. Several new procedures for the Suzuki cross-coupling reaction, the activation of aryl chlorides, the functionaliz…

A Simple Phosphine–Diolefin‐Promoted Copper‐Catalysed N‐Arylation of Pyrazoles with (Hetero)aromatic Bromides: The Case of Chloroarenes Revisited

A molecularly defined new phosphine–diolefin cubane copper pre-catalyst used at 1.25 mol % under mild conditions promotes the coupling of pyrazoles to functionalised aryl and heteroaryl bromides, which hold a variety of functional groups. This versatile phosphorus-based system was thus successfully used, under identical conditions, for the coupling of a large scope of heteroaromatics to selectively produce pyridinyl- and pyrimidinyl-pyrazoles, as well as several novel furyl-, thienyl- and thiazolyl-substituted pyrazoles. The careful investigation of coupling with the analogous aryl and heteroaryl chlorides clearly indicated that for specifically activated chloroarenes a direct nucleophilic …

CCDC 1054568: Experimental Crystal Structure Determination

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CCDC 1433505: Experimental Crystal Structure Determination

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CCDC 922383: Experimental Crystal Structure Determination

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CCDC 1532854: Experimental Crystal Structure Determination

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CCDC 1828692: Experimental Crystal Structure Determination

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CCDC 1433497: Experimental Crystal Structure Determination

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CCDC 1908608: Experimental Crystal Structure Determination

Related Article: Clève D. Mboyi, Delphine Vivier, Ahmad Daher, Paul Fleurat-Lessard, Hélène Cattey, Charles H. Devillers, Claire Bernhard, Franck Denat, Julien Roger, Jean-Cyrille Hierso|2020|Angew.Chem.,Int.Ed.|59|1149|doi:10.1002/anie.201911947

CCDC 1908609: Experimental Crystal Structure Determination

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CCDC 1433499: Experimental Crystal Structure Determination

Related Article: Fatima Allouch, Nejib Dwadnia, Nikolay V. Vologdin, Yurii V. Svyaschenko, Hélène Cattey, Marie-José Penouilh, Julien Roger, Daoud Naoufal, Ridha Ben Salem, Nadine Pirio, Jean-Cyrille Hierso|2015|Organometallics|34|5015|doi:10.1021/acs.organomet.5b00601

CCDC 988195: Experimental Crystal Structure Determination

Related Article: Matthieu Beaupérin, Radomyr Smaliy, Hélène Cattey, Philippe Meunier, Jun Ou, Patrick H. Toy, Jean-Cyrille Hierso|2014|Chem.Commun.|50|9505|doi:10.1039/C4CC04307C

CCDC 881688: Experimental Crystal Structure Determination

Related Article: Vincent Rampazzi, Alexandre Massard, Philippe Richard, Michel Picquet, Pierre Le Gendre, Jean-Cyrille Hierso|2012|ChemCatChem|4|1828|doi:10.1002/cctc.201200368

CCDC 1485963: Experimental Crystal Structure Determination

Related Article: Nejib Dwadnia, Julien Roger, Nadine Pirio, Hélène Cattey, Ridha Ben Salem, Jean-Cyrille Hierso|2017|Chem.Asian J.|12|459|doi:10.1002/asia.201601583

CCDC 1532860: Experimental Crystal Structure Determination

Related Article: Emmanuel Lerayer, Patrice Renaut, Julien Roger, Nadine Pirio, Hélène Cattey, Charles H. Devillers, Dominique Lucas, Jean-Cyrille Hierso|2017|Chem.Commun.|53|6017|doi:10.1039/C7CC02469J

CCDC 980179: Experimental Crystal Structure Determination

Related Article: Nejib Dwadnia, Fatima Allouch, Nadine Pirio, Julien Roger, Hélène Cattey, Sophie Fournier, Marie-Josée Penouilh, Charles H. Devillers, Dominique Lucas, Daoud Naoufal, Ridha Ben Salem, and Jean-Cyrille Hierso|2013|Organometallics|32|5784|doi:10.1021/om400317s

CCDC 980175: Experimental Crystal Structure Determination

Related Article: Nejib Dwadnia, Fatima Allouch, Nadine Pirio, Julien Roger, Hélène Cattey, Sophie Fournier, Marie-Josée Penouilh, Charles H. Devillers, Dominique Lucas, Daoud Naoufal, Ridha Ben Salem, and Jean-Cyrille Hierso|2013|Organometallics|32|5784|doi:10.1021/om400317s

CCDC 1828690: Experimental Crystal Structure Determination

Related Article: Clève D. Mboyi, Delphine Vivier, Ahmad Daher, Paul Fleurat-Lessard, Hélène Cattey, Charles H. Devillers, Claire Bernhard, Franck Denat, Julien Roger, Jean-Cyrille Hierso|2020|Angew.Chem.,Int.Ed.|59|1149|doi:10.1002/anie.201911947

CCDC 2077804: Experimental Crystal Structure Determination

Related Article: Petr Vosáhlo, Léa Radal, Marine Labonde, Ivana Císařová, Julien Roger, Nadine Pirio, Jean-Cyrille Hierso, Petr Štěpnička|2021|Organometallics|40|1934|doi:10.1021/acs.organomet.1c00244

CCDC 1433506: Experimental Crystal Structure Determination

Related Article: Fatima Allouch, Nejib Dwadnia, Nikolay V. Vologdin, Yurii V. Svyaschenko, Hélène Cattey, Marie-José Penouilh, Julien Roger, Daoud Naoufal, Ridha Ben Salem, Nadine Pirio, Jean-Cyrille Hierso|2015|Organometallics|34|5015|doi:10.1021/acs.organomet.5b00601

CCDC 1433503: Experimental Crystal Structure Determination

Related Article: Fatima Allouch, Nejib Dwadnia, Nikolay V. Vologdin, Yurii V. Svyaschenko, Hélène Cattey, Marie-José Penouilh, Julien Roger, Daoud Naoufal, Ridha Ben Salem, Nadine Pirio, Jean-Cyrille Hierso|2015|Organometallics|34|5015|doi:10.1021/acs.organomet.5b00601

CCDC 1433501: Experimental Crystal Structure Determination

Related Article: Fatima Allouch, Nejib Dwadnia, Nikolay V. Vologdin, Yurii V. Svyaschenko, Hélène Cattey, Marie-José Penouilh, Julien Roger, Daoud Naoufal, Ridha Ben Salem, Nadine Pirio, Jean-Cyrille Hierso|2015|Organometallics|34|5015|doi:10.1021/acs.organomet.5b00601

CCDC 1433498: Experimental Crystal Structure Determination

Related Article: Fatima Allouch, Nejib Dwadnia, Nikolay V. Vologdin, Yurii V. Svyaschenko, Hélène Cattey, Marie-José Penouilh, Julien Roger, Daoud Naoufal, Ridha Ben Salem, Nadine Pirio, Jean-Cyrille Hierso|2015|Organometallics|34|5015|doi:10.1021/acs.organomet.5b00601

CCDC 2089400: Experimental Crystal Structure Determination

Related Article: Tuan-Anh Nguyen, Marie-Jose�� Penouilh, He��le��ne Cattey, Nadine Pirio, Paul Fleurat-Lessard, Jean-Cyrille Hierso, Julien Roger|2021|Organometallics|40|3571|doi:10.1021/acs.organomet.1c00465

CCDC 1433504: Experimental Crystal Structure Determination

Related Article: Fatima Allouch, Nejib Dwadnia, Nikolay V. Vologdin, Yurii V. Svyaschenko, Hélène Cattey, Marie-José Penouilh, Julien Roger, Daoud Naoufal, Ridha Ben Salem, Nadine Pirio, Jean-Cyrille Hierso|2015|Organometallics|34|5015|doi:10.1021/acs.organomet.5b00601

CCDC 1405174: Experimental Crystal Structure Determination

Related Article: Tuan-Anh Nguyen, Marie-Jose�� Penouilh, He��le��ne Cattey, Nadine Pirio, Paul Fleurat-Lessard, Jean-Cyrille Hierso, Julien Roger|2021|Organometallics|40|3571|doi:10.1021/acs.organomet.1c00465

CCDC 1532862: Experimental Crystal Structure Determination

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CCDC 1474154: Experimental Crystal Structure Determination

Related Article: Emmanuel Lerayer, Patrice Renaut, Stéphane Brandès, Hélène Cattey, Paul Fleurat-Lessard, Ghenwa Bouhadir, Didier Bourissou, and Jean-Cyrille Hierso|2017|Inorg.Chem.|56|1966|doi:10.1021/acs.inorgchem.6b02510

CCDC 2089403: Experimental Crystal Structure Determination

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CCDC 1993888: Experimental Crystal Structure Determination

Related Article: Clève D. Mboyi, Ahmad Daher, Neelab Khirzada, Charles H. Devillers, Hélène Cattey, Paul Fleurat-Lessard, Julien Roger, Jean-Cyrille Hierso|2020|New J.Chem.|44|15235|doi:10.1039/D0NJ02338H

CCDC 1405175: Experimental Crystal Structure Determination

Related Article: Tuan-Anh Nguyen, Marie-Jose�� Penouilh, He��le��ne Cattey, Nadine Pirio, Paul Fleurat-Lessard, Jean-Cyrille Hierso, Julien Roger|2021|Organometallics|40|3571|doi:10.1021/acs.organomet.1c00465

CCDC 1009630: Experimental Crystal Structure Determination

Related Article: Vincent Rampazzi, Julien Roger, Régine Amardeil, Marie-José Penouilh, Philippe Richard, Paul Fleurat-Lessard, and Jean-Cyrille Hierso|2016|Inorg.Chem.|55|10907|doi:10.1021/acs.inorgchem.6b01318

CCDC 1438419: Experimental Crystal Structure Determination

Related Article: Vincent Rampazzi, Julien Roger, Régine Amardeil, Marie-José Penouilh, Philippe Richard, Paul Fleurat-Lessard, and Jean-Cyrille Hierso|2016|Inorg.Chem.|55|10907|doi:10.1021/acs.inorgchem.6b01318

CCDC 1009631: Experimental Crystal Structure Determination

Related Article: Vincent Rampazzi, Julien Roger, Régine Amardeil, Marie-José Penouilh, Philippe Richard, Paul Fleurat-Lessard, and Jean-Cyrille Hierso|2016|Inorg.Chem.|55|10907|doi:10.1021/acs.inorgchem.6b01318

CCDC 1875843: Experimental Crystal Structure Determination

Related Article: Oana Moncea, Juan Casanova-Chafer, Didier Poinsot, Lukas Ochmann, Clève D. Mboyi, Houssein O. Nasrallah, Eduard Llobet, Imen Makni, Molka El Atrous, Stéphane Brandès, Yoann Rousselin, Bruno Domenichini, Nicolas Nuns, Andrey A. Fokin, Peter R. Schreiner, Jean-Cyrille Hierso|2019|Angew.Chem.,Int.Ed.|58|9933|doi:10.1002/anie.201903089

CCDC 1009244: Experimental Crystal Structure Determination

Related Article: Andrey A. Fokin, Raisa I. Yurchenko, Boryslav A. Tkachenko, Natalie A. Fokina, Maria A. Gunawan, Didier Poinsot, Jeremy E. P. Dahl , Robert M. K. Carlson , Michael Serafin , Hélène Cattey, Jean-Cyrille Hierso , and Peter R. Schreiner|2014|J.Org.Chem.|79|5369|doi:10.1021/jo500793m

CCDC 1908612: Experimental Crystal Structure Determination

Related Article: Clève D. Mboyi, Delphine Vivier, Ahmad Daher, Paul Fleurat-Lessard, Hélène Cattey, Charles H. Devillers, Claire Bernhard, Franck Denat, Julien Roger, Jean-Cyrille Hierso|2020|Angew.Chem.,Int.Ed.|59|1149|doi:10.1002/anie.201911947

CCDC 943311: Experimental Crystal Structure Determination

Related Article: Anatolyi Marchenko, Anastasiya Hurieva, Heorgii Koidan, Vincent Rampazzi, Hélène Cattey, Nadine Pirio, Aleksandr N. Kostyuk, and Jean-Cyrille Hierso|2012|Organometallics|31|5986|doi:10.1021/om300563n

CCDC 1485958: Experimental Crystal Structure Determination

Related Article: Nejib Dwadnia, Julien Roger, Nadine Pirio, Hélène Cattey, Ridha Ben Salem, Jean-Cyrille Hierso|2017|Chem.Asian J.|12|459|doi:10.1002/asia.201601583

CCDC 1991440: Experimental Crystal Structure Determination

Related Article: Clève D. Mboyi, Ahmad Daher, Neelab Khirzada, Charles H. Devillers, Hélène Cattey, Paul Fleurat-Lessard, Julien Roger, Jean-Cyrille Hierso|2020|New J.Chem.|44|15235|doi:10.1039/D0NJ02338H

CCDC 980177: Experimental Crystal Structure Determination

Related Article: Nejib Dwadnia, Fatima Allouch, Nadine Pirio, Julien Roger, Hélène Cattey, Sophie Fournier, Marie-Josée Penouilh, Charles H. Devillers, Dominique Lucas, Daoud Naoufal, Ridha Ben Salem, and Jean-Cyrille Hierso|2013|Organometallics|32|5784|doi:10.1021/om400317s

CCDC 922384: Experimental Crystal Structure Determination

Related Article: Fatima Allouch, Nikolay V. Vologdin, Hélène Cattey, Nadine Pirio, Daoud Naoufal, Ali Kanj, Radomyr V. Smaliy, Aleksandr Savateev, Anatoly Marchenko, Anastasia Hurieva, Heorgii Koidan, Aleksandr N. Kostyuk, Jean-Cyrille Hierso|2013|J.Organomet.Chem.|735|38|doi:10.1016/j.jorganchem.2013.03.025

CCDC 1532856: Experimental Crystal Structure Determination

Related Article: Emmanuel Lerayer, Patrice Renaut, Julien Roger, Nadine Pirio, Hélène Cattey, Charles H. Devillers, Dominique Lucas, Jean-Cyrille Hierso|2017|Chem.Commun.|53|6017|doi:10.1039/C7CC02469J

CCDC 1558706: Experimental Crystal Structure Determination

Related Article: Johan Guilbaud, Marine Labonde, Hélène Cattey, Sylvie Contal, Christian Montalbetti, Nadine Pirio, Julien Roger, Jean-Cyrille Hierso|2017|Adv.Synth.Catal.|359|3792|doi:10.1002/adsc.201700858

CCDC 1477185: Experimental Crystal Structure Determination

Related Article: Julien Roger, Sylviane Royer, Hélène Cattey, Aleksandr Savateev, Radomyr V. Smaliy, Aleksandr N. Kostyuk, Jean-Cyrille Hierso|2017|Eur.J.Inorg.Chem.||330|doi:10.1002/ejic.201600502

CCDC 2077807: Experimental Crystal Structure Determination

Related Article: Petr Vosáhlo, Léa Radal, Marine Labonde, Ivana Císařová, Julien Roger, Nadine Pirio, Jean-Cyrille Hierso, Petr Štěpnička|2021|Organometallics|40|1934|doi:10.1021/acs.organomet.1c00244

CCDC 1828691: Experimental Crystal Structure Determination

Related Article: Clève D. Mboyi, Delphine Vivier, Ahmad Daher, Paul Fleurat-Lessard, Hélène Cattey, Charles H. Devillers, Claire Bernhard, Franck Denat, Julien Roger, Jean-Cyrille Hierso|2020|Angew.Chem.,Int.Ed.|59|1149|doi:10.1002/anie.201911947

CCDC 1405170: Experimental Crystal Structure Determination

Related Article: Tuan-Anh Nguyen, Marie-Jose�� Penouilh, He��le��ne Cattey, Nadine Pirio, Paul Fleurat-Lessard, Jean-Cyrille Hierso, Julien Roger|2021|Organometallics|40|3571|doi:10.1021/acs.organomet.1c00465

CCDC 980178: Experimental Crystal Structure Determination

Related Article: Nejib Dwadnia, Fatima Allouch, Nadine Pirio, Julien Roger, Hélène Cattey, Sophie Fournier, Marie-Josée Penouilh, Charles H. Devillers, Dominique Lucas, Daoud Naoufal, Ridha Ben Salem, and Jean-Cyrille Hierso|2013|Organometallics|32|5784|doi:10.1021/om400317s

CCDC 1532855: Experimental Crystal Structure Determination

Related Article: Emmanuel Lerayer, Patrice Renaut, Julien Roger, Nadine Pirio, Hélène Cattey, Charles H. Devillers, Dominique Lucas, Jean-Cyrille Hierso|2017|Chem.Commun.|53|6017|doi:10.1039/C7CC02469J

CCDC 922386: Experimental Crystal Structure Determination

Related Article: Fatima Allouch, Nikolay V. Vologdin, Hélène Cattey, Nadine Pirio, Daoud Naoufal, Ali Kanj, Radomyr V. Smaliy, Aleksandr Savateev, Anatoly Marchenko, Anastasia Hurieva, Heorgii Koidan, Aleksandr N. Kostyuk, Jean-Cyrille Hierso|2013|J.Organomet.Chem.|735|38|doi:10.1016/j.jorganchem.2013.03.025

CCDC 1559130: Experimental Crystal Structure Determination

Related Article: Clève D. Mboyi, Ahmad Daher, Neelab Khirzada, Charles H. Devillers, Hélène Cattey, Paul Fleurat-Lessard, Julien Roger, Jean-Cyrille Hierso|2020|New J.Chem.|44|15235|doi:10.1039/D0NJ02338H

CCDC 943312: Experimental Crystal Structure Determination

Related Article: Anatolyi Marchenko, Anastasiya Hurieva, Heorgii Koidan, Vincent Rampazzi, Hélène Cattey, Nadine Pirio, Aleksandr N. Kostyuk, and Jean-Cyrille Hierso|2012|Organometallics|31|5986|doi:10.1021/om300563n

CCDC 1009245: Experimental Crystal Structure Determination

Related Article: Andrey A. Fokin, Raisa I. Yurchenko, Boryslav A. Tkachenko, Natalie A. Fokina, Maria A. Gunawan, Didier Poinsot, Jeremy E. P. Dahl , Robert M. K. Carlson , Michael Serafin , Hélène Cattey, Jean-Cyrille Hierso , and Peter R. Schreiner|2014|J.Org.Chem.|79|5369|doi:10.1021/jo500793m

CCDC 1054567: Experimental Crystal Structure Determination

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CCDC 986896: Experimental Crystal Structure Determination

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CCDC 2089401: Experimental Crystal Structure Determination

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CCDC 1908611: Experimental Crystal Structure Determination

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CCDC 1405627: Experimental Crystal Structure Determination

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CCDC 980174: Experimental Crystal Structure Determination

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CCDC 1908610: Experimental Crystal Structure Determination

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CCDC 980176: Experimental Crystal Structure Determination

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CCDC 1438417: Experimental Crystal Structure Determination

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CCDC 1908606: Experimental Crystal Structure Determination

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CCDC 2089402: Experimental Crystal Structure Determination

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CCDC 2077806: Experimental Crystal Structure Determination

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CCDC 2089404: Experimental Crystal Structure Determination

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CCDC 1902394: Experimental Crystal Structure Determination

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CCDC 1433502: Experimental Crystal Structure Determination

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CCDC 1908607: Experimental Crystal Structure Determination

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CCDC 1405168: Experimental Crystal Structure Determination

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CCDC 922385: Experimental Crystal Structure Determination

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CCDC 1828689: Experimental Crystal Structure Determination

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CCDC 1433500: Experimental Crystal Structure Determination

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CCDC 2077802: Experimental Crystal Structure Determination

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CCDC 1532861: Experimental Crystal Structure Determination

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CCDC 1433507: Experimental Crystal Structure Determination

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CCDC 1009629: Experimental Crystal Structure Determination

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CCDC 1405169: Experimental Crystal Structure Determination

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CCDC 2089399: Experimental Crystal Structure Determination

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CCDC 1485961: Experimental Crystal Structure Determination

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CCDC 1559132: Experimental Crystal Structure Determination

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CCDC 943313: Experimental Crystal Structure Determination

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CCDC 1054565: Experimental Crystal Structure Determination

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CCDC 1902395: Experimental Crystal Structure Determination

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CCDC 1054566: Experimental Crystal Structure Determination

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CCDC 1532859: Experimental Crystal Structure Determination

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CCDC 1438418: Experimental Crystal Structure Determination

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CCDC 1009243: Experimental Crystal Structure Determination

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CCDC 988196: Experimental Crystal Structure Determination

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CCDC 1559131: Experimental Crystal Structure Determination

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CCDC 2077801: Experimental Crystal Structure Determination

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CCDC 943310: Experimental Crystal Structure Determination

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CCDC 980180: Experimental Crystal Structure Determination

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CCDC 1474155: Experimental Crystal Structure Determination

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CCDC 1532857: Experimental Crystal Structure Determination

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CCDC 902497: Experimental Crystal Structure Determination

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CCDC 2077803: Experimental Crystal Structure Determination

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CCDC 2077805: Experimental Crystal Structure Determination

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CCDC 1485959: Experimental Crystal Structure Determination

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CCDC 1485960: Experimental Crystal Structure Determination

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CCDC 980181: Experimental Crystal Structure Determination

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CCDC 2089405: Experimental Crystal Structure Determination

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CCDC 1433508: Experimental Crystal Structure Determination

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CCDC 1405171: Experimental Crystal Structure Determination

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CCDC 1485962: Experimental Crystal Structure Determination

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CCDC 1054569: Experimental Crystal Structure Determination

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