Search results for "polymer"

Nickel as a Lewis Base in a T‐Shaped Nickel(0) Germylene Complex Incorporating a Flexible Bis(NHC) Ligand

2018

Flexible, chelating bis(NHC) ligand 2, able to accommodate both cis- and trans-coordination modes, was used to synthesize (2)Ni(η 2 -cod), 3. In reaction with GeCl2, this produced (2)NiGeCl2, 4, featuring a T-shaped Ni(0) and a pyramidal Ge center. Complex 4 could also be prepared from [(2)GeCl]Cl, 5, and Ni(cod)2, in a reaction that formally involved Ni-Ge transmetalation, followed by coordination of the extruded GeCl2 moiety to Ni. A computational analysis showed that 4 possesses considerable multiconfigurational character and the Ni→Ge bond is formed through σ-donation from the Ni 4s, 4p, and 3d orbitals to Ge. (NHC)2Ni(cod) complexes 9 and 10, as well as (NHC)2GeCl2 derivative 11, incor…

Phospholylmethano P-chirogenic-phosphine-borane as P-(η2-BH3)-chelating ligands of rhodium (I): Synthesis, characterization and asymmetric hydrogenat…

2021

International audience; The stereoselective synthesis of new phospholylmethano P-chirogenic-phosphine-borane was achieved by P-C bond formation of the bridge, using electrophilic or nucleophilic P*-building blocks. These P1CH2P2*.BH3 ligands behaved as chelating (κ1-P1)-(η2-BH3) entities towards the cationic rhodium(I) centre. The resulting chiral rhodium complexes were tested in asymmetric rhodium catalyzed hydrogenation of methyl 2-(acetamido)acrylate.

Electrochemistry and spectroelectrochemistry of heterobimetallic porphyrin-corrole dyads. Influence of the spacer, metal ion, and oxidation state on …

2005

Combined electrochemical and UV-visible spectroelectrochemical methods were utilized to elucidate the prevailing mechanisms for electroreduction of previously synthesized porphyrin-corrole dyads of the form (PCY)H2Co and (PCY)MClCoCl where M = Fe(III) or Mn(III), PC = porphyrin-corrole, and Y is a bridging group, either biphenylenyl (B), 9,9-dimethylxanthenyl (X), anthracenyl (A), or dibenzofuranyl (O). These studies were carried out in pyridine, conditions under which the cobalt(IV) corrole in (PCY)MClCoCl is immediately reduced to its Co(III) form, thus enabling direct comparisons with the free-base porphyrin dyad, (PCY)H2Co(III) under the same solution conditions. The compounds are all r…

1977

Copolymers from styrene and 1-vinylimidazoles (4a–f), form low spin adducts with iron(II) porphyrins and iron(III) porphyrins, when the content of imidazolyl groups in the polymer is ten mole percent or more. With polymers having a content of imidazolyl groups of less then one mole percent, only high spin adducts are observed. With terpolymers, in which the porphyrin is covalently bound to the copolymer the same phenomenon is observed. Only the high spin Fe(II) porphyrin adducts in the solid state adsorb molecular oxygen like cobalt(II) porphyrins under the same conditions. Adsorptions and desorptions of oxygen are much slower in the cases of iron(II) porphyrins than with the cobalt(II) por…

Influence of Acidic Support in Metallocene Catalysts for Ethylene Polymerization

2001

Abstract We studied a ZSM-5 zeolite as metallocene support for ethylene polymerization. We transformed the Na-ZSM-5 into H-ZSM-5. After the cation exchange, the zeolite was calcined at three different temperatures. Characterization of the material indicated that by means of the calcination procedure it is possible to produce dealuminization with an increase in extraframework aluminum (EFAL). We prepared zirconocene-supported catalysts on zeolitic supports using two preparation methods. The higher activity was observed with the zirconocene supported on ZSM-5 pretreated at 900°C. We think that the dealuminization process generates an increase in EFAL. This EFAL is responsible for the higher a…

Imidotungsten(VI) complexes with chelating phenols as ROMP catalysts

2011

Abstract Tungsten(VI) complexes of the type [W(NPh)Cl3(L)] (L = chelating phenolate) were studied as catalyst precursors for ROMP of 2-norbornene, dicyclopentadiene and 5-vinyl-2-norbornene. These compounds form active catalysts when treated by ethyl magnesium bromide. Moreover, polymerisations can be run under ambient atmosphere without complicated inert atmosphere techniques. Synthesis and crystal structure of a new precursor complex [W(NPh)Cl3(LS)] (LS = 2,4-di-tert-butyl-6-(phenylthiomethyl)phenolate) are also described.

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

2010

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.

Synthesis of novel fluorinated building blocks via halofluorination and related reactions.

2020

A study exploring halofluorination and fluoroselenation of some cyclic olefins, such as diesters, imides, and lactams with varied functionalization patterns and different structural architectures is described. The synthetic methodologies were based on electrophilic activation through halonium ions of the ring olefin bonds, followed by nucleophilic fluorination with Deoxo-Fluor®. The fluorine-containing products thus obtained were subjected to elimination reactions, yielding various fluorine-containing small-molecular entities.

Proximity Effect using a Nanocage Structure: Polyhedral Oligomeric Silsesquioxane-Imidazolium Tetrachloro- palladate Salt as a Precatalyst for the Su…

2016

A polyhedral oligomeric silsesquioxane-imidazolium tetrachloropalladate salt (POSS-Imi-PdCl4) was prepared by the reaction of a polyhedral oligomeric silsesquioxane-imidazolium chloride salt (POSS-Imi-Cl) with PdCl2 and used as a pre-catalyst for the Suzuki-Miyaura reaction in water at 100 °C at a low loading (0.08-0.16 mol %). Biphenyl compounds were isolated in high to excellent yields. A comparison of the POSS-based catalyst with the corresponding catalyst without the nanocage structure (i.e., 1-butyl-3-methylimidazolium tetrachloropalladate) highlighted the role of the POSS structure to reach higher yields in the Suzuki-Miyaura reaction. This result is ascribed to a proximity effect of …

Templating effect of carbon nanoforms on highly cross-linked imidazolium network: Catalytic activity of the resulting hybrids with Pd nanoparticles

2019

Two different carbon nanoforms (CNFs), namely multi-walled carbon nanotubes (MWCNTs) and carbon nanohorns (CNHs), have been chosen as support for the direct polymerization of a bis-vinylimidazolium salt. Transmission electron microscopy analyses revealed a templating effect of the CNFs on the growth of the polymeric network, which perfectly covers their whole surfaces creating a cylindrical or spherical coating for MWCNTs and CNHs, respectively. Subsequently, the CNFs-polyimidazolium have been used as stabilizers for Pd nanoparticles (Pd NPs), and the obtained materials have been characterized by means of analytical and spectroscopic techniques and then employed as easily recoverable and re…