1,721,164 research outputs found

    Supported catalysts from polymerizable transition metal complexes

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    This review covers the last 12 years of research on the synthesis and use of heterogeneous catalysts obtained by co-polymerization of suitable metal containing monomers (MCM). The catalytic applications of these supported metal complexes are subdivided into three areas. Hydrogenation of alkenes and functionalized olefins are covered first. Oxidation of several substrates such as olefins, sulfides, alcohols, and aldehydes are then considered. Of particular interest in this framework is the use of chiral salen metal containing monomers for the stereoselective epoxidation of hindered olefins. Alkene and alkyne polymerizations, Heck and Heck-type reactions, allylic alkylation, and Michael additions are discussed in the field of carbon-carbon bond forming reactions. A common factor emerging from this survey is the application of metal containing monomers for the synthesis of molecularly imprinted polymers to be used as catalysts or catalyst supports

    Polymer Supported Catalysts Obtained from Metal-Containing Monomers

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    This review summarizes the progress made in the last eight years on the synthesis and use in catalysis of polymer supported metal complexes obtained by co-polymerization of metal-containing monomers (MCMs) with suitable co-monomers and cross-linkers. These materials are divided into four important classes: microporous organic polymers, molecularly imprinted polymers (MIPs), macropouros organic polymers, polymers obtained by ring opening metathesis polymerization (ROMP). Although the MIPs have essentially a macroporous structure, they constitute a separate group of catalysts for their peculiar way of synthesis. The discussion focuses on the efficiency and reusability of all these potentially recoverable catalysts

    A Pd(AcO)2/t-Bu3P/K3PO4 catalytic system for the control of Suzuki cross-coupling polymerisation

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    The initiation of the Suzuki cross-coupling polymerisation with a fluorene-based AB-type monomer was finely tuned within the chain-growth regime by the suitable control of the species generated by the Pd(AcO)2/t-Bu3P/K3PO4 catalytic system. The prototypical poly(9,9-di-n-octyl-fluorene) was obtained with extremely fast (1 min) polymerisation rates, excellent polydispersities (1.16) and molecular weights dependent on the monomer/catalyst molar ratio, without the need to resort to formal chain-initiators

    Chloride based ionic liquids as promoting agents for Meerwein reaction in solventless conditions

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    Chloride based ionic liquids were used as chloride source in Meerwein reaction either in [bmin]X (bmim = 1-butyl-3methylimidazolium, X = BF4, PF6) as solvents or in solventless conditions. Satisfactory yields (49-71%) with diversely substituted diazonium salts were achieved by using 1,3-dibutylimidazoliurn chloride in the presence of a bimetallic Zn/Cu catalyst

    Reactions of a phosphinito bridged diplatinum(I) complex with coinage metal electrophiles

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    We have recently described the synthesis of the complex [(PHCy2)Pt1(m-PCy2){k2P,O-m-P(O)Cy2}Pt2(PHCy2)] (Pt-Pt) (1), the first unsymmetrical phosphinito bridged Pt(I) species.[1] The phosphinito bridge differentiates the charge distributions on the two platinum atoms as confirmed by NMR spectroscopy (dPt(1) = -4798 ppm, dPt(2) = -5207 ppm) and DFT studies. Complex 1 shows a rich chemistry as it reacts with nucleophiles [PHCy2, PCy3, P(S)HCy2],[2] protic species HX [P(OH)Cy2, PhSH, HF, HCl, HBr, HI, HBF4],[3, 4] and small molecules such as H2.[5] Recently, we started investigations on the reactivity of complex 1 towards Au and Ag based electrophiles. In this communication, it will be shown that, differently from the isolobal H+ (which attacks the phosphinito oxygen and migrates onto the Pt-Pt bond),3 the [Ag(PPh3)]+ electrophile attacks complex 1 selectively to the Pt2-mP bond to afford the cationic cluster [(PHCy2)Pt1(m-PCy2){k2P,O-m-P(O)Cy2}Pt2{m- -Ag(PPh3)}(PHCy2)]+ (Pt–Pt) (2+) in which the [Ag(PPh3)]+ moiety bridges the mP-Pt2 bond. Analogous reactivity is observed also when phosphane free electrophiles such as AgOTf, AgBF4, AgClO4 and AgCl are used. Moreover, the reactivity of 1 towards Au(I) electrophiles such as AuCl and [Au(PPh3)Cl] was dependent on the reagent and on the experimental conditions. references: 1. Gallo, V.; Latronico, M.; Mastrorilli, P.; Nobile, C. F.; Suranna, G. P.; Ciccarella, G.; Englert, U.; Eur. J. Inorg. Chem., 2005, 4607–4616. 2. Gallo, V.; Latronico, M.; Mastrorilli, P.; Nobile, C. F.; Polini, F.; Re, N.; Englert, U.; Inorg. Chem., 2008, 47, 4785–4795. 3. Latronico, M.; Polini, F.; Gallo, V.; Mastrorilli, P; Calmuschi-Cula B.; Englert, U.; Re, N.; Repo T., Raisanen M.; Inorg. Chem., 2008, 47, 9979-9796. 4. M. Latronico, P. Mastrorilli, V. Gallo, M.M.Dell’Anna, F. Creati, N. Re, U. Englert, Inorg. Chem. 2011, 50, 3539–3558 5. Mastrorilli P., Latronico M., Gallo V., Polini F., Re N., Marrone A., Gobetto R., Ellena S.. J. Am. Chem. Soc. 2010, 132, 4752–476
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