Search results for "METHANE"
showing 10 items of 1763 documents
Self-assembly and anion encapsulation properties of cavitand-based coordination cages.
2001
Two novel classes of cavitand-based coordination cages 7a--j and 8a--d have been synthesized via self-assembly procedures. The main factors controlling cage self-assembly (CSA) have been identified in (i) a P--M--P angle close to 90 degrees between the chelating ligand and the metal precursor, (ii) Pd and Pt as metal centers, (iii) a weakly coordinated counterion, and (iv) preorganization of the tetradentate cavitand ligand. Calorimetric measurements and dynamic (1)H and (19)F NMR experiments indicated that CSA is entropy driven. The temperature range of the equilibrium cage-oligomers is determined by the level of preorganization of the cavitand component. The crystal structure of cage 7d r…
Optically active amphiphilic hyperbranched polyglycerols as templates for palladium nanoparticles
2006
Abstract We report a systematic study on the encapsulation of palladium nanoparticles in optically active amphiphilic hyperbranched polyglycerols with different optical signs and different degrees of polymerization, namely (−)-P(G 40 C16 0.5 ) 1 and (+)-P(G 73 C16 0.5 ) 2 . Several issues have been addressed here: (a) relatively wide size distributions (1–5 nm) of palladium nanoparticles have been achieved, (b) a remarkable template effect ( 1 , DP n = 40, 1.2 ± 0.1 nm; 2 , DP n = 73, 2.3 ± 0.1 nm average particle size) has been observed using TEM technique, as shown by the particle size dependent on the degree of polymerization of the polymers, (c) NaBH 4 is found to be a convenient redu…
Stereoselective synthesis of carane-based chiral β- and γ-amino acid derivatives via conjugate addition
2015
Abstract Michael addition of dibenzylamine to (−)-tert-butyl isochaminate, prepared in three steps from (−)-perillaldehyde, furnished a carane-based β-amino acid derivative in a highly stereospecific reaction. The resulting amino ester was transformed to the bicyclic amino acid, a promising building block for the synthesis of 1,3-heterocycles and peptidomimetics. The conjugate addition of nitromethane to α,β-unsaturated methyl ester likewise resulted in nitro esters in stereospecific reactions. Catalytic reduction of the nitro group yielded a γ-amino ester. Under acidic conditions, the hydrolysis of the methyl ester resulted in an unexpected aminolactone-type product through rearrangement o…
Enhanced Sieving of C2‐Hydrocarbon from Methane by Fluoro‐Functionalization of In‐MOF with Robust Stability
2021
Developing efficient adsorbent materials is crucial for adsorption and separation to realize the purification of energy source and raw chemicals. Here, we report a novel and robust 3D In-based MOF built up with fluorine-functionalized ligands, QMOF-2F, with improved separation properties of C2-light hydrocarbons over methane at room temperature respect isoreticular non-fluorinated MOF. QMOF-2F shows a remarkable chemical stability in different solvents, including water, and pH (2-12). DFT calculations support the key role of fluorine-functionalization on the improved performance of QMOF-2F.
Counterion-Mediated Crossing of the Cyanine Limit in Crystals and Fluid Solution: Bond Length Alternation and Spectral Broadening Unveiled by Quantum…
2020
Absorption spectra of cyanine⊕·Br⊖ salts show a remarkable solvent dependence in non/polar solvents, exhibiting narrow, sharp band shapes in dichloromethane but broad features in toluene; this chan...
Pollutant Adsorbtion and Detection: Methyl-Substituted α-Cyclodextrin as Affinity Material for Storage, Separation, and Detection of Trichlorofluorom…
2018
The cover image depicts the hazard caused by chlorofluorocarbons such as CFC‐11, which are used, for example, as blowing agents for polyurethane foams, and the protective effect of the oligosaccharide, hexakis‐(2,3,6‐tri‐O‐methyl)‐α‐cyclodextrin, which is capable of binding CFC‐11 by supramolecular complexation and thus protecting the stratospheric ozone layer from the harmful trichlorofluoromethane. Further details can be found in article number 1800057 by Ralf Hellmann, Siegfried R. Waldvogel, and co‐workers.
Electrically conductive TCNQ complexes of aromatic ionenes
1995
New types of complex salts of 7,7',8,8'-tetracyanoquinodimethane with aromatic ionenes and their model compounds were prepared. The electrical conductivity and the activation energy were measured and discussed in relation to their structure. The effects of the nature of the aromatic unit, and the flexibility and rigidity of the polymer backbone were compared with the corresponding model compounds. The effects of frequency and temperature are discussed in terms of the molecular structure of the complex. The electroconductivity at room temperature of the 1 :1 polymer complex salts was found to be between 2 x 10 -4 and 7 x 10 -5 S/cm, while that of the model complex salts was between 1.3 x 10 …
Gold Redox Catalytic Cycles for the Oxidative Coupling of Alkynes
2011
[EN] Au(I)/Au(III) catalytic cycles are catalytically competent to perform the oxidative coupling of alkynes in the homogeneous phase at room temperature and without any protecting atmosphere. Selectfluor as oxidant, wet acetonitrile as solvent, and sodium carbonate as base are the reagents of choice. Both aromatic and alkyl alkynes can be coupled, and mechanistic studies reveal that at least two gold species having different oxidation states are implicated in the key step of the coupling.
Solvent-free ruthenium-catalysed triflate coupling as a convenient method for selective azole-o-C-H monoarylation.
2019
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.
Racemic and Optically Pure Heptahelicene-2-carboxylic Acid: Its Synthesis and Self-Assembly into Nanowire-Like Aggregates
2010
Heptahelicene-2-carboxylic acid was effectively synthesised from suitably functionalised naphthalene building blocks. Methoxy-substituted 1,1'-ethyne-1,2-diylbis(2-but-3-yn-1-ylnaphthalene) was cyclised in the presence of CpCo(CO)(2)/PPh(3) to 2-methoxy-7,8,11,12-tetrahydroheptahelicene, which was converted into heptahelicen-2-yl trifluoromethanesulfonate. This reactive intermediate underwent Pd(OAc)(2)/dppp-catalysed methoxycarbonylation reaction to provide, after hydrolysis, heptahelicene-2-carboxylic acid. The racemate was resolved into enantiomers by semipreparative HPLC on a chiral column. The helicity of (+)-(P)-heptahelicene-2-carboxylic acid was assigned by correlating its CD spectr…