Search results for "Hydrogen"

Reversible O–H bond activation by an intramolecular frustrated Lewis pair

2019

The interactions of the O-H bonds in alcohols, water and phenol with dimethylxanthene-derived frustrated Lewis pairs (FLPs) have been probed. Within the constraints of this backbone framework, the preference for adduct formation or O-H bond cleavage to give the corresponding zwitterion is largely determined by pKa considerations. In the case of the PPh2/B(C6F5)2 system and p-tBuC6H4OH, an equilibrium is established between the two isomeric forms which allows the thermodynamic parameters associated with zwitterion formation via O-H bond cleavage to be probed.

Ion-Pair Complexation with Dibenzo[21]Crown-7 and Dibenzo[24]Crown-8 bis-Urea Receptors

2016

Synthesis and ion-pair complexation properties of novel ditopic bis-urea receptors based on dibenzo[21]crown-7 (R(1) ) and dibenzo[24]crown-8 (R(2) ) scaffolds have been studied in the solid state, solution, and gas phase. In a 4:1 CDCl3 /[D6 ]DMSO solution, both receptors clearly show positive heterotropic cooperativity toward halide anions when complexed with Rb(+) or Cs(+) , with the halide affinity increasing in order I(-) <Br(-) <Cl(-) . In solution, the rubidium complexes of both receptors have higher halide affinities compared to the caesium complexes. However, Rb(+) and Cs(+) complexes of R(2) show stronger affinities toward all the studied anions compared to the corresponding catio…

Protonation of a Spherical Macrotricyclic Tetramine: Water Inclusion, Allosteric Effect, and Cooperativity

2017

The spherical macrotricyclic cryptand tetramine "C24" (1) displays remarkable protonation behaviour. It undergoes protonation in four successive steps for which pKa values of 11.17±0.05, 10.28±0.04, 6.00±0.06 and 3.08±0.08 have been determined at 298 K. The unusually close values for the first two protonations provide evidence for the encapsulation of a water molecule serving as effector for the second protonation, which is consistent with earlier observations that the exchange of protons bound in the diprotonated species with solvent protons is unusually slow and that 17 O NMR spectra show the presence of an oxygen centre in the same species quite distinct from that of solvent water. Encap…

A metal-free and regioselective approach to (Z)-β-fluorovinyl sulfones and their chemoselective hydrogenation to β-fluoroalkyl sulfones

2018

Abstract A highly regioselective, metal-free hydrofluorination reaction of alkynyl sulfones was developed using TBAF—one of the cheapest and most commonly available fluoride sources. In addition, the reactivity of the resulting β-fluorovinyl sulfones was studied, focusing on their selective hydrogenation reaction. Both β-fluorovinyl sulfones and their hydrogenation products β-fluoroalkyl sulfones may find applications in medicinal and agrochemical sciences.

Determining Factors for the Unfolding Pathway of Peptides, Peptoids, and Peptidic Foldamers.

2016

We present a study of the mechanical unfolding pathway of five different oligomers (α-peptide, β-peptide, δ-aromatic-peptides, α/γ-peptides, and β-peptoids), adopting stable helix conformations. Using force-probe molecular dynamics, we identify the determining structural factors for the unfolding pathways and reveal the interplay between the hydrogen bond strength and the backbone rigidity in the stabilization of their helix conformations. On the basis of their behavior, we classify the oligomers in four groups and deduce a set of rules for the prediction of the unfolding pathways of small foldamers.

Synthesis, crystal structure and magnetic properties of two oxalato-bridged dimetallic trinuclear complexes combined with a polar cation

2010

Two isostructural heterometallic trinuclear oxalato-bridged complexes of formula C(4)[MCr(2)(ox)(6)(H(2)O)(2)]·nH(2)O (C(+) = 4-aminopyridinium; ox(2-) = oxalate dianion; M(2+) = Mn(2+), n = 3, 1; M(2+) = Co(2+), n = 3.25, 2) have been synthesized by using direct self-assembly methods combining C(3)[Cr(ox)(3)] and the chloride salts of the corresponding metal ion. The crystal structures of both compounds have been resolved by single-crystal X-ray diffraction. They crystallize in the C2/c space group [a = 11.5113(15) Å, b = 20.250(3) Å, c = 21.810(4) Å, beta = 100.447(10) degrees, V = 5161.6(3) Å(3), and Z = 4 for 1, and a = 11.4334(16) Å, b = 20.243(2) Å, c = 21.805(3) Å, beta = 101.113(9) …

2016

The title compound, C32H48O8P2S2, was prepared by the nickel-catalyzed reaction of bis(5-bromothienyl)dipropoxybenzene and triisopropyl phosphite. The thiophene rings are inclined to the benzene ring by 14.6 (2) and 25.3 (3)°. One propyloxy group is disordered. Four hydrogen bonds connect the molecules, which are arranged in ribbons parallel to thebcplane.

Targeted delivery of hydrogen for the bioremediation of aquifers contaminated by dissolved chlorinated compounds.

2019

Dihydrogen (H2) gas injection is a promising option to enhance the reductive biodehalogenation of contaminants in groundwater. However, it is challenging to ensure its targeted delivery at the right places in plumes, and for the long times required for bioremediation. In this paper, the ability of surfactant foam to retain H2 in the saturated zone and to enhance its release in the dissolved form was compared to traditional biosparging. H2 gas was injected, either alone, or as foam, in a 2D saturated cell packed with glass beads. This cell was continuously flushed with deoxygenated water to mimic aquifer circulation, and H2 was studied both in terms of gas distribution in the cell and dissol…

Asynchronous changes of CO2, H2, and He concentrations in soil gases: A theoretical model and experimental results

2016

Lower mantle hydrogen partitioning between periclase and perovskite : a quantum chemical modelling

2016

Abstract Partitioning of hydrogen (often referred to as H2O) between periclase (pe) and perovskite (pvk) at lower mantle conditions (24–80 GPa) was investigated using quantum mechanics, equilibrium reaction thermodynamics and by monitoring two H-incorporation models. One of these (MSWV) was based on replacements provided by Mg2+ ↔ 2H+ and Si4+ ↔ 4H+; while the other (MSWA) relied upon substitutions in 2Mg2+ ↔ Al3+ + H+ and Si4+ ↔ Al3+ + H+. H2O partitioning in these phases was considered in the light of homogeneous (Bulk Silicate Earth; pvk: 75%–pe:16% model contents) and heterogeneous (Layered Mantle; pvk:78%–pe:14% modal contents) mantle geochemical models, which were configured for lower…