Search results for "hydrogen"
showing 10 items of 4254 documents
Can Green Dimethyl Carbonate Synthesis be More Effective? A Catalyst Recycling Study Benefiting from Experimental Kinetics and DFT Modeling
2014
Dibutyldimethoxystannanes are known to catalyze the reaction between carbon dioxide and methanol leading to dimethyl carbonate. Despite similarities between din-butyl- and ditert-butyldimethoxystannane, the recycled complexes have different structural features. In the din-butyl series, a decatin(IV) complex has been characterized and is less active than the stannane precursor. Kinetic experiments likely indicate that all the tin centers are not active, which is confirmed in comparing with the related dinuclear 1,3-dimethoxytetran-butyldistannoxane complex. In the ditert-butyl series, the tritin(IV) complex isolated upon recycling features the steric effect of bulky tBu ancillary ligands. In…
Conformational properties and folding analysis of a series of seven oligoamide foldamers
2016
33 crystal structures (11 unsolvated and 22 solvates) of a series of seven oligoamide foldamers were analysed. The crystal structures revealed that despite the structural and environmental differences the series of foldamers prefer only two general conformations, a protohelical @-conformation and a sigmoidal S-conformation. Both conformations also have preferred crystal packing motifs and solvate forming tendencies. Hydrogen bonding was found to be the most decisive factor in conformational preference, but steric properties, the type of the peripheral substituents, as well as solvent and aromatic interactions were also found to have an effect on the conformational details and crystal form. …
Benzyl ions from 1,1-(2,2′-dimethoxyphenyl)-substituted 2-methylpropanes under electron ionization
2006
The electron ionization (EI)-induced fragmentations of a series of 1,1-(2,2'-dimethoxyphenyl)-substituted 2-methylpropanes (1-20) in both 70 eV and mass-analyzed ion kinetic energy (MIKE) spectra have been investigated. The EI-MS spectra of these compounds are characterized by the presence of abundant benzyl ions. These ions result from competitive hydrogen migration from the 2- and 2'-methoxy groups on the carbenium center of the diphenylmethyl cations formed by benzylic cleavage of the molecular ions. The relative abundances of the benzyl ions arising from such competitive processes are discussed and rationalized. The steric effect of the 3- or 3'-substituents is the main discriminating f…
Evidence that steric factors modulate reactivity of tautomeric iron-oxo species in stereospecific alkane C-H hydroxylation
2014
A new iron complex mediates stereospecific hydroxylation of alkyl C-H bonds with hydrogen peroxide, exhibiting excellent efficiency. Isotope labelling studies provide evidence that the relative reactivity of tautomerically related oxo-iron species responsible for the C-H hydroxylation reaction is dominated by steric factors This work has been supported by the European Union (the Erasmus Mundus program), the International Research Training Group Metal Sites in Biomolecules: Structures, Regulation and Mechanisms (www.biometals.eu), and COST Action CM1003. M.C. acknowledges ERC-29910, MINECO of Spain for CTQ2012- 37420-C02-01/BQU and CSD2010-00065, catalan DIUE (2009SGR637) and an ICREA academ…
Synthesis, crystal and molecular-electronic structure, and kinetic investigation of two new sterically hindered isomeric forms of the dimethyl[methyl…
2017
Two new structural isomers – 2,4-dimethyl-5-[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride (1) and 2,4-dimethyl-3-[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride (2) were synthesized by interaction of N-(2,4-dimethylphenyl)-N-methyl-benzenesulfonamide or N-(2,6-dimethylphenyl)-N-methylbenzenesulfonamide with chlorosulfonic acid. Both compounds have been structurally characterized by X-ray single crystal diffraction at 100 K. The crystals of 1 are triclinic: space group View the MathML source, a = 8.1542(2), b = 11.0728(3), c = 11.2680(3) Å, α = 116.557(3), β = 95.155(2), γ = 108.258(2)°, V = 831.97(4) Å3, Z = 2, R = 0.0251 for 2429 reflections; the crystals of 2 are monoclinic:…
Synthesis and structural characterisation of bulky heptaaromatic (hetero)aryl o-substituted s-aryltetrazines
2020
An expedient two-step synthesis produces in good yield polyaromatic heptacyclic (hetero)arylated o-substituted s-aryltetrazines (s-Tz) directly from diphenyl s-tetrazine. This methodology overcomes the steric limitations of classical Pinner-like syntheses encountered for o-functionalized s-Tz. A single step palladium-catalyzed N-directed C–H bond tetrahalogenation is followed by a Pd-catalyzed Suzuki (hetero)arylation that is achieved simultaneously on four sites. The single crystal X-ray diffraction structure of the resulting typical polyaromatic heptacyclic aromatic compound 3,6-bis(2,6-diphenyl)-1,2,4,5-tetrazine (3) is analyzed, together with R-functionalized peripheral phenyl derivativ…
A Self-Sorting Scheme Based on Tetra-Urea Calix[4]arenes
2009
Size and shape do matter: When dimerized in nonpolar solvents, an equimolar mixture of eleven tetra-urea calix[4]arenes with different wide-rim substituents self-sorts into only six out of 35 different homo- and heterodimers (see picture). Since the calixarene scaffold and the four urea units are the same in all cases, the self-sorting process is driven only by the cooperative action of steric requirements and stoichiometry.
Association of 2-acylaminopyridines and benzoic acids. Steric and electronic substituent effect studied by XRD, solution and solid-state NMR and calc…
2013
Abstract Eight single crystal X-ray structures, solid-state NMR spectroscopic, and theoretical studies utilizing QTAIM methodology were used to characterize the 2-acyl (alkyl in acyl = methyl, ethyl, t-butyl, and 1-adamantyl) amino-6-R-pyridine/4-R′-benzoic acid (R,R′ = H or Me) cocrystals. As expected among alkyl groups 1-adamantyl due to its bulkiness has the most significant effect on the relative positions of molecules in cocrystals. In addition, the subtle electronic and steric effects by the methyl substituents were observed. The theoretical calculations with full geometry optimizations are in agreement with the experimental findings (geometry, energy of hydrogen bonds). Based on the …
Energy interactions in amyloid-like fibrils from NNQQNY.
2014
We use large-scale MP2 calculations to analyze the interactions appearing in amyloid fibers, which are difficult to determine experimentally. To this end, dimers and trimers of the hexapeptide NNQQNY from the yeast prion-like protein Sup35 were considered as model systems. We studied the energy interactions present in the three levels of organization in which the formation of amyloid fibrils is structured. The structural changes in the hydrogen bonds were studied too. It was found that the most energetic process is the formation of the β-sheet, which is equally due to both hydrogen bonds and van der Waals interactions. The aromatic rings help stabilize these aggregates through stacking of t…
Molecular Recognition via Hydrogen Bonding at the Air−Water Interface: An Isotherm and Fourier Transform Infrared Reflection Spectroscopy Study
1997
Molecular recognition in Langmuir monolayers at the air−water interface as a function of headgroup orientation and substrate using isotherms and in-situ Fourier transform infrared (FT-IR) reflection spectroscopy has been investigated. Isotherm measurements show that urea and 2,4,6-triaminopyrimidine (TAP) are specifically bound to barbituric acid lipid monolayers. As expected, TAP causes a larger shift in the limiting area of the isotherms than urea due to steric requirements. The peak positions of the CH stretching vibrations of the barbituric acid lipids indicate that the alkyl chains of barbituric acid lipids 1−3 are in a close-packed all-trans conformation both before and after the reco…