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A practical preparation of the reagent PMDTALi using a super base system under mild conditions has been developed. This PMDTALi base has been demonstrated to be a very efficient reagent for the lithiation of bridged alkenes via direct deprotonation. Further reactions with electrophiles and also coupling reactions in the presence of Pd catalysts provide the bridged alkenes with a broad range of functional groups including silyl, alkyl, halogen and aryl substituents. The utilization of this new lithium reagent has brought a new diversity to the choice of lithium reagent for the deprotonation of synthetically challenging systems.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Herein, we report the syntheses, spectral and structural characterization, and magnetic behavior of four new dinuclear terephthalato-bridged copper(II) complexes with formulae [Cu2(trpn)2(mu-tp)](ClO 4)2·2H2O (1), [Cu2(aepn) 2(mu-tp)(ClO4)2] (2), [Cu2(Medpt) 2(mu-tp)(H2O)2](ClO4)2 (3) and [Cu2(Et2dien)2(mu-tp)(H 2O)](ClO4)2 (4) where tp = terephthalate dianion, trpn = tris(3-aminopropyl)-amin, aepn = N-(2-aminoethyl)-1,3- propanediamine, Medpt = 3,3?-diamino-N-methyldipropylmine and Et 2dien = N,N-diethyldiethylenetriamine. The structures of these complexes consist of two mu-tp bridging Cu(II) centers in a bis(monodentate) bonding fashion. The coordination geometry of the Cu(II) ions in these compounds may be described as close to square-based pyramid (SP) with severe significant distortion towards trigonal bipyramid (TBP) stereochemistry in 1. The visible spectra of the complexes in aqueous solutions are in complete agreement with the assigned X-ray geometry around the Cu(II) centers. Also, the solid infrared spectral data for the stretching frequencies of the tp-carboxalato groups, the nu(COO-) reveals the existence of bis(monodentate) coordination mode for the bridged terephthalate ligand. The susceptibility measurements at variable temperature over the range 2-300 K are reported. Despite the same bonding mode of the tp bridging ligand, there has been observed slight antiferromagnetic coupling for the compounds 1 and 4 with J values of -0.5 and -2.9 cm3 K mol-1, respectively, and very weak ferromagnetic coupling for 2 and 3 with J values of 0.8 and 10.1 cm3 K mol-1, respectively. The magnetic results are discussed in relation to other related mu-terephthalato dinuclear Cu(II) published compounds.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Zwitterionization of multiwalled carbon nanotubes (ZCNTs) is initially conducted by grafting poly(4-styrenesulfonic acid) and poly(4-vinylpyridine) copolymers via an atom transfer radical polymerization (ATRP) reaction, and the products obtained are further used as an aqueous additive to fabricate thin-film nanocomposite (TFN) nanofiltration (NF) membranes. The most optimal membrane with a ZCNT dosage of 0.01%, Z-TFN 0.01% shows nearly 31% enhancement in water permeability (14.9 ± 0.5 L m-2 h-1 bar-1), probably due to the shortened ZCNT, which could create a larger number of inorganic-organic interfaces in the barrier layers. Besides, it also exhibits MgSO4/NaCl selectivity (5.6 ± 0.8), 2.8 times higher than that of the pristine one (2.0 ± 0.2), which is attributed to the formation of ion-response channels and the stretching effect of the side chains. By using model brackish water as the feed solution and subjecting it to a two-stage NF process, the outstanding separation ability of the Z-TFN 0.01% membrane for the ions with the final Na+/Mg2+ concentration ratio in the permeate reaching as high as 589.2, as against only 111.7 for the control, is displayed. Furthermore, due to the strong bacteriostasis ability of quaternary ammonium compounds, Z-TFN 0.01% also shows excellent antibacterial properties, as evidenced by the mortality of Escherichia coli to 97% after remaining in contact with the membrane surface.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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An efficient synthesis of 5-organotellanyl-1H-1,2,3-triazole compounds was accomplished through [3+2] cycloaddition reaction of organic azides and (organotellanyl)alkynes. Additionally, 5-organotellanyl-1H-1,2,3-triazoles were readily functionalized at the 5-position by using a Sonogashira cross-coupling reaction, leading to highly functionalised triazoles. The regiochemistry of the products was assessed by two-dimensional NMR spectroscopic experiments and X-ray crystallography. An efficient synthesis of 5-organotellanyl-1H-1,2,3-triazole compounds through [3+2] cycloaddition reaction of organic azides and (organotellanyl)alkynes is presented. The 5-organotellanyl-1H-1,2,3-triazoles were readily functionalized at the 5-position to give highly functionalized triazoles. Copyright

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Surface-initiated polymerizations were carried out from polymeric surfaces of commercially important polyester films, poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN). These plastic films were modified prior to polymerization by plasma oxidation, exposing surface hydroxyl groups, in order to immobilise patterned self assembled monolayers (SAMs) of trichlorosilane initiator, through the soft lithographic method of microcontact printing (muCP). Subsequently, polymerizations were initiated from the surface via controlled atom transfer radical polymerization (ATRP), under aqueous conditions, to create patterned brushes of the thermo-responsive polymer poly(N-isopropyl acrylamide) (PNIPAM). By creating patterned, rather than homogeneous brushes characterization was made possible by atomic force microscopy (AFM).

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A facile Atom Transfer Radical Polymerization (ATRP) method based on the use of the complex obtained with CuCl, CuCl2 and the very active ligand 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (Me6CyClam) as catalytic system, was successfully employed for the first time to polymerize vinyl acetate (VAc) with a good control over the polymerization, which showed a living character and monomer conversion up to 90%. The use of such an active ligand allows to maintain a particularly low concentration of propagating species once very reactive radicals, from such monomers, are formed, hence establishing a fast and dynamic ATRP equilibrium. Several kinetic studies on the ATRP of VAc were carried out with the aim to identify the optimized conditions allowing a good control over the process attaining materials with well-defined structure and low polydispersity. The livingness of the macromolecular system was confirmed, among the others, by using the obtained PVAc as ATRP macroinitiator for the synthesis of several block copolymers. Furthermore, the possibility to hydrolyse the VAc block thus attaining amphiphilic materials was studied.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 3030-47-5, molcular formula is C9H23N3, introducing its new discovery. Safety of N1-(2-(Dimethylamino)ethyl)-N1,N2,N2-trimethylethane-1,2-diamine

Reaction of (1) with N,N,N’,N”,N”-pentamethyldiethylenetriamine (PMDETA) in diethylether (Et2O) gives (2).The complex has been characterized by DTA analysis, 1H and 13C NMR spectroscopy and X-ray crystallography.The thermal properties and the structures of 2 and (3) indicate the significant difference of the influence of PMDETA and N,N,N’,N’-tetramethylethylenediamine (TMEDA) on the platinacyclopentane system.Key words: Lithium; Platinum

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Copper polyamine complexes are among the most utilized catalysts for controlled radical polymerization reactions. Copper(I) complexes may react reversibly with an alkyl halide to form an alkyl radical, which promotes polymerization, and a copper(II) halido complex in a step known as activation. The kinetics of the reverse reaction between the alkyl radical and higher oxidation-state copper complex (deactivation) are less studied because these reactions approach diffusion-controlled rates, and it is difficult to isolate or quantify the concentration of the alkyl radical (R·) in situ. Herein we report a broadly applicable electrochemical technique for simultaneously measuring the kinetics of deactivation and kinetics of activation.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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This work was conducted as part of our continuing effort to determine the factors that affect cation formation for organometallic aluminum complexes. In this study, the interactions of R2AlX (where R = Me, iBu, tBu; X = Cl, Br, I) with the monodentate bases thf, pyridine, NEt3, HNiPr2, H2NiBu, H2NtBu, and O=PPh3 are examined to determine the role of the base in cation formation. These reactions resulted in the neutral adducts of the general form R2AlX-base (1-6, 8, 10, and 12) as well as the cationic complexes [R2Al(base)2]X (7, 9, and 11). The reactions of Me2AlX (where X = Cl, Br) with PMDETA (N,N?,N?,N?-pentamethyldiethylenetriamine) and the catalytic activity of the resulting cationic complexes (13 and 14) are also discussed. All of the compounds were characterized by mp, IR, 1H-NMR, and elemental analyses, and in one an X-ray crystallographic study was carried out. X-ray data for 13: triclinic, P1, a = 6.9542(6) A, b = 12.2058(10) A, c = 13.2417(11) A, alpha = 106.236(2), beta = 98.885(2), gamma = 93.807(2), V = 1059.06(15) A3, and Z = 2 for 181 parameters refined on 4358 reflections having F > 6.0sigma(F), R = 0.0697, and Rw = 0.0697.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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AB amphiphilic comb-like block copolymers of poly(oligo[ethylene glycol] methyl ether methacrylate) and polydimethylsiloxane were synthesised with a methodology based on atom transfer radical polymerization (ATRP). The anionic ring opening polymerisation of hexamethylcyclotrisiloxane followed by reaction with 3-(chlorodimethylsilyl) propyl 2-bromo-2-methylpropanoate propyldimethylchlorosilane gave suitable macroinitiators for the ATRP of oligo[ethylene glycol] methyl ether methacrylate. The latter synthetic procedure was optimised by performing a number of syntheses varying the reaction solvent, catalytic complex and the temperature used. Copolymers with relatively high polydispersity indices (Mw/Mn>1.3) could be synthesised at room temperature by employing a Cu(I)Br:N,N,N?,N?,N?- pentamethyldiethylenetriamine complex in n-propanol with Cu(II)Br. The optimum reaction conditions employed a Cu(I)Cl:N-(n-propyl)-2-pyridyl(methanimine) complex with an n-propanol/water mixture or toluene as solvent at 90C. This gave block copolymers of the desired molecular weights and polydispersity indices of less than 1.1. The block copolymers were characterised with 1H NMR and 13C NMR spectroscopy and size exclusion chromatography.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI