ChemPlusChem

Description

ChemPlusChem is a peer-reviewed journal tailored to multidisciplinary chemistry and materials researchers from across the world. Fully comprehensive in its scope, ChemPlusChem publishes original papers covering at least two different aspects (subfields) of chemistry or one of chemistry and one of another scientific discipline (one chemistry topic plus another one, hence the title ChemPlusChem).

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  • ISSN
    2192-6506

Publications in this journal

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    ABSTRACT: As the workhorses for many applications, neutral dimeric μ2-X-bridged diphosphine rhodium complexes of the type [{Rh(diphosphine)(μ2-X)}2] (X=Cl, OH) are usually prepared in situ by the addition of diphosphine ligands to the rhodium complex [{Rh(diolefin)(μ2-X)}2] (diolefin=cyclooctadiene (cod) or norbornadiene (nbd)) or [{Rh(monoolefin)2(μ2-Cl)}2] (monoolefin=cyclooctene (coe) or ethylene (C2H4)). The in situ procedure has been investigated for the diphosphines 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP), 5,5′-bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole (SEGPHOS), 5,5′-bis[di(3,5-xylyl)phosphino]-4,4′-bi-1,3-benzodioxole (DM-SEGPHOS), 5,5′-bis[di(3,5-di-tert-butyl-4-methoxyphenyl)phosphino]-4,4′-bi-1,3-benzodioxole (DTBM-SEGPHOS), 2,2′-bis(diphenylphosphino)-1,1′-dicyclopentane (BICP), 1-[2-(diphenylphosphino)ferrocenyl]ethyldi-tert-butylphosphine (PPF-PtBu2), 1,1′-bis(diisopropylphosphino)ferrocene (DiPPF), 1,2-bis(diphenylphosphino)ethane (DPPE), 1,2-bis(o-methoxyphenylphosphino)ethane (DIPAMP), 4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxalane (DIOP), 1,2-bis(2,5-dimethylphospholano)benzene (Me-DuPHOS), 1,4-bis(diphenylphosphino)butane (DPPB), and 1,3-bis(diphenylphosphino)propane (DPPP); the resulting complexes have been characterized by 31P NMR spectroscopy and, in most cases, also by X-ray analysis. Depending on the diphosphine ligand, the solvent, the temperature, and the rhodium precursor, species other than the desired one [{Rh(diphosphine)(μ2-X)}2] are formed, for example, [(diolefin)Rh(μ2-Cl)2Rh(diphosphine)], [Rh(diphosphine)(diolefin)]+, [Rh(diphosphine)2]+, and [Rh(diphosphine)(diolefin)(Cl)]. The results clearly show that the in situ method commonly applied for precatalyst preparation cannot be regarded as an optimal strategy for the formation of such neutral [{Rh(diphosphine)(μ2-X)}2] complexes.
    ChemPlusChem 09/2014;
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    ABSTRACT: The synthesis of vinyl chloride from acetylene by hydrochlorination has gained tremendous interest in coal-based chemistry. Bimetallic gold–cesium(I)/activated carbon (AuCsI/AC) catalysts were found to have a higher catalytic activity and stability for acetylene hydrochlorination when compared with gold catalysts. Over 1 Au4 CsI/AC catalysts, the maximum conversion of acetylene was 94 % and there was only 5 % C2H2 conversion loss after 50 h of running time. Moreover, the 1 Au4 CsI/AC catalyst delivered a stable performance during a 500 h test with the conversion of acetylene and the selectivity of vinyl chloride reaching more than 99.8 and 99.9 %, respectively. Temperature-programmed reduction of H2, temperature-programmed desorption of C2H2, and X-ray photoelectron spectroscopy techniques were further applied to detect structural information on the AuCsI/AC catalysts. Additives of CsCl indeed stabilized the catalytically active Au3+ species and inhibited the reduction of Au3+ to Au0, thereby improving the activity and long-term stability of gold-based catalysts.
    ChemPlusChem 09/2014;
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    ABSTRACT: The investigation of the vanadium electrolyte stability issue on the molecular-level solvation structure and the dynamics has led to the successful designing of mixed acid-based vanadium electrolytes. This new mixed-acid based electrolyte system render approximately 70 % increase in energy density (≈40 Wh L−1) and approximately 80 % increase in stable temperature window (−10 to +50 °C) compared with conventional sulfuric acid-based vanadium electrolyte. Through a comprehensive study by density functional theory and nuclear magnetic resonance spectroscopies, the improved stability is attributed to the hydrochloric acid as optimal cosolvent providing chloride anions for a ligand-exchange process in the vanadium solvation structure. The role of the chloride counteranion in the solvation structure and dynamics of vanadium species was studied using combined magnetic resonance spectroscopy and DFT-based theoretical methods. The solvation phenomenon of multiple vanadium species and their impact on vanadium redox flow battery electrolyte chemical stability are discussed.
    ChemPlusChem 09/2014;
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    ABSTRACT: Cadmium sulfide and oxide hexagonal nanoplates were prepared by a facile ion-exchange strategy and crystal transformation process by using morphology-analogous cadmium oxyhydroxide as a precursor. The precursors of uniform Cd(OH)2 hexagonal nanoplates was first synthesized by a simple ethylenediaminetetraacetic acid disodium salt assisted hydrothermal method. Then, through ion-exchange reactions of the as-prepared Cd(OH)2 precursors with S2− anions, cubic-phase CdS was formed immediately on the surface of Cd(OH)2 nanoplates. The above intermediates could be further completely converted into CdS and CdO nanoplates without morphology changes through thermal treatment at 280 °C for 4 h under a sulfur atmosphere and under air, respectively. The photocatalytic activity of all samples was evaluated by the photocatalytic decolorization of an aqueous solution of methylene blue and photocatalytic hydrogen production under visible-light irradiation. The results show that the CdS hexagonal nanoplates exhibit high visible-light photocatalytic degradation properties and photocatalytic hydrogen production activity. The enhanced visible-light photocatalytic activity can be related to several factors, including a suitable band gap, phase structure, and morphology of the hexagonal nanoplates.
    ChemPlusChem 09/2014;
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    ABSTRACT: Successful surface modification of iron oxide nanoparticles is crucial for their usage in applications. However, ligand exchange methods introducing siloxanes have several drawbacks. Presented here is a novel approach for the surface modification of iron oxide nanoparticles by making use of siloxanes, synthesized by thiol-ene click chemistry, with protected functional groups. Afterwards the ligands are deprotected to liberate their functionality. This approach solves the issues related to ligand orientation and colloidal stability during surface modification.
    ChemPlusChem 09/2014;
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    ABSTRACT: The synthesis of L-lysine-based amphiphilic hydrogelator consisting of a naphthalene moiety at the N termini and an ethyleneoxy unit with free primary amine at the C terminus is reported. The amphiphile showed good gelation ability with minimum gelation concentration 0.6 % w/v in binary mixtures of dimethyl sulfoxide/phosphate buffer (1:4 v/v, pH 7.4). The hydrogel was characterised by spectroscopic and microscopic studies to delineate the role of non-covalent interactions in self-assembly gelation. Subsequently, Ag nanoparticles were synthesised within the hydrogel by in situ photo-reduction of AgNO3 under sunlight, in which the gelators act as reducing/stabilising agents. The nanocomposites were characterised by transmission electron microscopy, UV/Vis and X-ray diffraction spectroscopy and thermogravimetric analysis. Rheology of the soft nanocomposite showed significant mechanical strength and thixotropic self-recovery properties, which made the composite suitable for use as a syringe-injectable hydrogel. These soft nanocomposites exhibited excellent antibacterial activity against both Gram-positive and Gram-negative bacteria. They showed low haemolytic activity and high biocompatibility to mammalian (Chinese hamster ovarian) cells. In addition, agar–gelatin film infused with these nanocomposites allowed normal growth of mammalian cells on its surface while being lethal towards bacteria.
    ChemPlusChem 09/2014;
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    ABSTRACT: The preparation of ZnO films by a versatile and effective facing-target sputtering method under various sputtering pressures is described. The ZnO films are coated with an ultrathin (2 nm) Pt layer through dc diode sputtering to form hybrid Pt/ZnO photocatalytic films. Interestingly, the Pt/ZnO films show an efficient visible-light photoresponse for the decomposition of gas-phase methanol owing to the unique surface plasmon resonance of the Pt film.
    ChemPlusChem 09/2014;
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    ABSTRACT: Treatment of cis-[Ru(bpy)2Cl2]⋅2 H2O or Δ/Λ-[Ru(bpy)2(py)2]2+ (bpy=2,2′-bipyridine, py=pyridine) with the prochiral thioether ligands 2-alkylthiobenzoic acid (HOSR) produces the corresponding thioether complexes rac-[Ru(bpy)2(OSR)](PF6) (R=Me (rac-1), iPr (rac-2), 2-benzylthiobenzonate (Bn) (rac-3)) and Δ/Λ-[Ru(bpy)2(OSR)](PF6) (R=Me (Δ-1/Λ-1), iPr (Δ-2/Λ-2), Bn (Δ-3/Λ-3)) with retention of the configurations at chiral metal centers. In situ oxidation of the thioether complexes by meta-chloroperoxybenzoic acid provides the corresponding sulfoxide complexes rac-[Ru(bpy)2(OSOR)](PF6) (OSOR is 2-alkylsulfinylbenzonate, R=Me (rac-1 a), iPr (rac-2 a), Bn (rac-3 a)), Δ-[Ru(bpy)2{(R)-OSOR}](PF6) (R=Me (Δ-1 a), iPr (Δ-2 a), Bn (Δ-3 a)), and Λ-[Ru(bpy)2{(S)-OSOR}](PF6) (R=Me (Λ-1 a), iPr (Λ-2 a), Bn (Λ-3 a)) in yields of 95 % with 98 % ee values. The absolute configurations at the metal centers and sulfur atoms were determined by means of X-ray crystallography. The results indicate that the configurations of the metal centers are retained and have the function of controlling sulfoxide chirality during the oxidation process. The Δ metal-centered configuration enantioselectively generates an R-configuration sulfoxide, and the Λ configuration enantioselectively forms an S-configuration sulfoxide in the course of the in situ oxidation reaction, thereby resulting in a predetermined chirality of the sulfoxide ligands. The predetermined chirality of sulfoxides (S)-HOSOR and (R)-HOSOR were obtained by the treatments of the corresponding sulfoxide complexes Δ-[Ru(bpy)2{(R)-OSOR}](PF6) and Λ-[Ru(bpy)2{(S)-OSOR}](PF6) with trifluoroacetic acid in yields of 90 % with 83.5–92.9 % ee values.
    ChemPlusChem 09/2014;
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    ABSTRACT: A new flexible nanostructure of [CoFe2O4/PVP]@[YAG:7 %Tb3+/PVP] magnetic-luminescent bifunctional coaxial nanofibers is fabricated successfully by electrospinning technology using a homemade coaxial spinneret. The morphologies, structures, and magnetic and luminescent properties of the final products are investigated by modern determination techniques. The results show that the coaxial nanofibers simultaneously provide better magnetic and luminescent properties than CoFe2O4/YAG:7 %Tb3+/PVP composite nanofibers owing to the isolation of the YAG:7 %Tb3+ luminescent nanofibers from the CoFe2O4 magnetic nanofibers. Furthermore, the luminescent characteristics and saturation magnetizations of the coaxial nanofibers can be tuned by adjusting the contents of luminescent and magnetic compounds. The formation mechanism of coaxial nanofibers is also presented. More importantly, the design concept and construction technology are of universal significance for the fabrication of other bifunctional coaxial nanofibers.
    ChemPlusChem 09/2014;
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    ABSTRACT: 4-Hydroxy-3-methoxyphenyl (MOP) and 2,3-dihydrobenzofuran-5-yl (DHB) groups were tested as potential new oxidizable labels for electrochemical detection of DNA. The corresponding 5-aryl-cytosine and 7-aryl-7-deazaadenine 2′-deoxyribonucleoside triphosphates (dNTPs) were prepared by the Suzuki coupling of halogenated dNTPs or by triphosphorylation of modified nucleosides, and were incorporated enzymatically into DNA by polymerase. In parallel, the electrochemical behavior of the labeled nucleosides, nucleotides, and DNA was studied to show that most of them give analytically useful signals of oxidation on the carbon electrode. Particularly, MOP appears to be a useful oxidizable DNA label since it offers independent detection of the modified DNA.
    ChemPlusChem 09/2014;
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    ABSTRACT: A series of O- or N-cinnamoylated, p-coumaroylated, feruloylated, phenyl, and substituted phenylpropiolated derivatives of L-malic, 3-hydroxypentanedioic, and L-glutamic acids were synthesized as analogues of the natural product glycogen phosphorylase (GP) inhibitor FR258900 (2,3-bis(4-hydroxycinnamoyloxy)glutaric acid). These compounds proved practically inactive against rabbit muscle glycogen phosphorylase b. A structure–activity study involving previously synthesized tartaric acid analogues of FR258900 revealed that two acyl moieties must be present in the compounds to make a good inhibitor. Molecular modeling methods (docking and quantitative structure–activity relationship (QSAR) calculations) were used to understand the nature of the binding affinities of these GP inhibitors. The generated 3D models for GP–inhibitor complexes showed that both the polar allosteric site pocket and the hydrophobic pocket at the interface of the homodimeric units of GP were important for effective binding of the acyl and aromatic moieties of the inhibitors. The predictive QSAR models consist of empirical and quantum mechanics descriptors and provide good explanatory and predictive abilities (prediction coefficient Q2=0.7–0.9 when cross-validation procedures were performed).
    ChemPlusChem 09/2014;
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    ABSTRACT: This study describes the solvent-dependent conversion of an oxime under identical reaction conditions ([Cu(bipy)Cl2]/NaN3/5-Br-H2salox/TEA=1:2:1:2 molar ratio; bipy=2,2′-bipyridyl, 5-Br-H2salox=5-bromosalicylaldoxime, TEA=triethylamine), but in different solvents. In DMSO/CH2Cl2 (2:1 v/v) only tetrazole is formed, whereas iminoacylation in MeCN and simple complexation takes place in MeOH. The formed tetrazole and iminoacylated ligands further undergo complexation with metal ions, as evidenced from single-crystal X-ray diffraction studies and ESI-MS analyses. Mechanistic models have been proposed in which coordination-assisted bonding of sodium azide across the CNOH double bond occurs to form a tetrazole and oxime–MeCN coupling forms an iminoacylated ligand. The former is a catalytic reaction, as evidenced from a turnover number of approximately 50, whereas the latter is stoichiometric in nature. This is the first report to demonstrate the dependence of solvent polarity on oxime transformation reactions through structural elucidation.
    ChemPlusChem 09/2014;
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    ABSTRACT: A series of soluble metal ethylxanthate compounds was synthesised as precursors for metal sulfide thin films to be deposited using solution-based techniques. Initially, a range of air- and moisture-stable organic ethylxanthate (EtXn) salts were synthesised (cation=Me4N (1), Et4N (2), Pr4N (3), Ph4P (4), guanidinium (5), NMeH3 (6), NMe2H2 (7), NMe3H (8), NH4 (9)). Thermogravimetric analysis (TGA) was used to examine their decomposition profiles, which in turn informed the decision of which counter cation was best suited for inclusion in the metal xanthate compounds. Periodic NMR spectroscopy studies and single-crystal X-ray diffraction (SXRD) were used to determine the role protic ammonium counter cations play in the detrimental conversion of xanthates to dithiocarbamate anions. The organic salts 1 and 4 were used to form the metal ethylxanthate compounds (Me4N)[M(EtXn)x] (x=3 for M=Cd (10 Cd), Ni (10 Ni), Zn (10 Zn); x=4 for M=La (11 La)) and (Ph4P)[M(EtXn)3] (M=Cd (12 Cd), Ni (12 Ni), Zn (12 Zn)). Solubility studies on these compounds were performed using a range of solvents to demonstrate the viability of using these compounds for solution-based deposition methods for thin-film formation. TGA of the metal xanthate compounds was used to examine their thermal-decomposition profiles and the product resulting from thermolysis was found to be the respective metal sulfide. In addition, the coproducts of thermal decomposition were analysed by headspace gas-chromatography mass spectrometry (HS GC–MS) to probe the decomposition mechanism of the precursors. In situ variable-temperature synchrotron XRD studies on both bulk and thin-film samples of 10 Cd and 12 Cd were used to examine metal sulfide crystalline phase formation. Decomposition of both precursors was found to give CdS in a hexagonal phase, with the addition of CdCl2 found to aid in increasing the crystallite size during crystallisation.
    ChemPlusChem 09/2014;
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    ABSTRACT: Multiwalled carbon nanotubes (CNTs) functionalized by oxygen plasma were used as a support for platinum–ruthenium nanoparticles for electrochemical methanol oxidation. The influence of plasma treatment time on the electrocatalytic activity was investigated by cyclic voltammetry, CO stripping voltammetry, and chronoamperometry. The electrocatalysts were characterized by Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The results showed that oxygen plasma treatment led to the formation of CO and COO groups on the CNT surface. Platinum–ruthenium nanoparticles dispersed with an optimum plasma treatment time of 30 min exhibited the maximum catalytic activity towards methanol oxidation. The rationale for the high catalytic activity is discussed.
    ChemPlusChem 09/2014;
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    ABSTRACT: Metal–air batteries are one important aspect of many in moving beyond lithium-ion research efforts. However, as our understanding of how molecular oxygen can act as a rechargeable cathode has progressed, the problems associated with how these materials at various states of charge interact with the lithium-metal anode are only beginning to come to the surface. In this study we have devised a method to coat the surface of lithium with a functional group to act as either an anchor for further derivation studies or be polymerized to create a nanometer-thick polymer coating attached to the surface by silane groups. These stable films, formed by polymerization of vinyl substituents, lower cell impedance at the electrode and over the first 50 cycles, increase cycling efficiency, and demonstrate lower-capacity fade.
    ChemPlusChem 09/2014;
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    ABSTRACT: Ferrofluids (FFs) or magnetic nanofluids are incredible smart materials consisting of ultrafine magnetic nanoparticles suspended in a liquid carrier medium, which exhibit both fluidity and magnetic controllability. Studies involving the dynamics and physicochemical properties of these magnetic nanofluids are an interdisciplinary area of research attracting researchers from different fields of science and technology. Herein, a comprehensive Review on the different aspects of FF research is presented. First, the synthesis and stabilization of various types of FFs are discussed followed by their physicochemical features such as polydispersity, magnetic behavior, dipolar interactions, formation of chainlike aggregates, and long-range ordering. The Review also details the rheological and thermal properties, dynamic instabilities, phase behavior, and particle assemblies in FFs to form complex multipolar geometries, photonic nanostructures, labyrinth structures, thin films, and droplets. Many important characterization techniques for probing FF properties are also briefly discussed, and the numerous innovative applications and future prospects of FFs are outlined.
    ChemPlusChem 09/2014;
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    ABSTRACT: A series of metal–organic coordination polymers based on two isomeric semirigid bis-pyridyl–bis-amide ligands and 5-methylisophthalic acid (5-H2MIP), namely, [Cu(3-bpah)(5-MIP)]⋅2 H2O (1), [Ni(3-bpah)(5-MIP)]⋅H2O (2), [Co(3-bpah)(5-MIP)]⋅H2O (3), [Cu(4-bpah)(5-MIP)(H2O)] (4), [Ni(4-bpah)(5-MIP)(H2O)]⋅H2O (5), [Co(4-bpah)(5-MIP)] (6), [Zn(4-bpah)(5-MIP)] (7), and [Cd(4-bpah)(5-MIP)] (8) (3-bpah=N,N′-bis(3-pyridinecarboxamide)-1,2-cyclohexane, 4-bpah=N,N′-bis(4-pyridinecarboxamide)-1,2-cyclohexane), have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction, thermogravimetric analysis, and single-crystal X-ray diffraction analyses. The title coordination polymers display versatile structural features with one-, two-, and three-dimensional frameworks. Complex 1 exhibits a two-dimensional (4,4) network named as type c, which is constructed from the arched 3-bpah and 5-MIP anions with alternating orientations. Complexes 2 and 3 show similar three-dimensional frameworks, which feature a trinodal (2,3,5)-connected topology with the Schläfli symbol of (42⋅6⋅84⋅102⋅12)(42⋅6)(8). Complex 4 exhibits an undulated two-dimensional (4,4) network of type b, in which the twist angles of the ligands are different from those of 1. Complex 5 reveals a one-dimensional double-strand chain, whereas complexes 6–8 exhibit similar two-dimensional double-layer structures with (42⋅6)(43⋅6⋅84⋅102)(4) topology. The influence of semirigid bis-pyridyl–bis-amide ligands and central metals on the structures of the title complexes has been reported. The fluorescent sensing behaviors of complexes 7 and 8, and the electrochemical and photocatalytic properties of complexes 1–6 have also been investigated in detail.
    ChemPlusChem 09/2014;
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    ABSTRACT: Hierarchical SnO2/Fe2O3 hollow spheres are fabricated through the solvothermal method accompanied by a facile solution procedure in the absence of any surfactant. The composition, crystalline structure, morphology, and electrochemical properties of the synthesized product are investigated systematically. The SnO2/Fe2O3 as an anode material in Li-ion batteries demonstrates a better reversible capacity and very good rate capability and cyclic performance compared with pure-phase SnO2 hollow spheres. The greatly enhanced Li-ion storage capability of the SnO2/Fe2O3 hollow spheres is believed to result from the synergy of the two materials, SnO2 and Fe2O3, which provides breathable aggregates for effective buffering of the drastic volume changes during the charge/discharge process. This work reports a promising method for the design and preparation of nanocomposite electrodes for Li-ion batteries.
    ChemPlusChem 09/2014;
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    ABSTRACT: 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 for immobilization”. These protected Cp fragments might also be of synthetic utility for generating other supported metallocenes. Tetra- and triphosphines were then formed and diversely functionalized for immobilization on virtually any kind of support. As evidenced by 31P NMR spectroscopy and the strong “through-space” spin–spin TSJ(P,P) coupling observed between P atoms, these modified polyphosphines induce, when immobilized on a support, a high local concentration of phosphorus donors that are spatially very close to each other (3–5 Å). These functionalized ligands have been incorporated into polystyrene to give either soluble or insoluble polymers and on inorganic supports such as silica. We report the catalytic performance at 0.05–0.5 mol % low palladium loading of the resulting immobilized polyphosphine ligands. This study provides proof-of-concept of supported catalytic materials built from modular polyphosphines with a novel approach to structurally controlled polydentate heterogeneous catalysts.
    ChemPlusChem 08/2014;

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