Search results for "Protonation"
showing 10 items of 583 documents
The Reductive σ Bond Cleavage of Barbaralane and 2,6‐Diphenylbarbaralane
1987
Barbaralane (2) and 2,6-diphenylbarbaralane (8) are synthesized in a straightforward way. The reductive cleavage of the strained hydrocarbons is achieved with alkali metals. The structure of the metallation products, in particular the bonding in the resulting allyl moieties, is elucidated by 1H- and 13C-NMR spectroscopy. The chemical behavior (oxidation, protonation, alkylation) sheds light on the modes of stabilization of the alkali metal derivatives. Die reduktive σ-Bindungsspaltung von Barbaralan und 2,6-Diphenylbarbaralan Barbaralan (2) und 2,6-Diphenylbarbaralan (8) werden auf rationelle Weise synthetisiert und die gespannten Kohlenwasserstoffe durch Reaktion mit Alkalimetallen redukti…
Synthesis of oligomeric chains with 9,10‐dihydroanthracene units by carbanion alkylation
1988
Deprotonation of 9,10-dihydroanthracene (2) affords the monoanion 6 which is subjected to alkylation reactions with mono and bifunctional electrophiles. Crucial intermediates in syntheses using 6 are 9-(3-bromopropyl)-9,10-dihydroanthracene (7) and 1,3-bis(9,10-dihydro-9-anthryl)propane (9) since they provide access to linear oligomers in which 9,10-dihydroanthracene units are linked by trimethylene groups. The alkylation processes of these species can be extended to the structurally related polymer 4. The regio- and stereoselectivity of the alkylation reactions are investigated by 1H- and 13C-NMR spectroscopy. Oligomere Ketten mit 9,10-Dihydroanthracen-Einheiten durch Carbanionalkylierung …
Supramolecular hydrogen-bonding tautomeric sulfonamido-phosphinamides: a perfect P-chirogenic memory
2011
P-chirogenic, supramolecular hydrogen-bonding C1-symmetrical sulfonamido–phosphinamides (METAMORPhos) have been successfully prepared. They were all found to possess a characteristic prototropic equilibrium between the PIII and the PV tautomers that is slow on the NMR spectroscopic timescale. Despite the dynamic and reversible protonation of the P centre, the P-chirogenic information was found to be retained in the tautomerization process, even in a protic solvent environment. Several strategies to access the corresponding enantiopure compounds were investigated, such as diastereoselective crystallization, or enantioselective synthesis. It was possible to resolve such a class of chiral liga…
Homo- and heterobinuclear Cu2+ and Zn2+ complexes of abiotic cyclic hexaazapyridinocyclophanes as SOD mimics
2013
The new receptor 3,7,11,15,19,23-hexaaza-1(2,6)-pyridinacyclotetracosaphane (L1) containing a complete sequence of propylenic chains has been synthesised. The acid–base behaviour and Cu2+ and Zn2+ coordination have been analysed by potentiometric measurements in 0.15 M NaClO4 for L1 and for the related compounds 3,7,11,14,18,22-hexaaza-1(2,6)-pyridinacyclotricosaphane (L2), 3,7,10,13,16,20-hexaaza-1(2,6)-pyridinacycloheneicosaphane (L3) and 3,7,10,12,15,19-hexaaza-1(2,6)-pyridinacycloicosaphane (L4). The crystal structure of [(CuH4L2)(H2O)(ClO4)](ClO4)5·3H2O shows an interesting combination of a metal ion coordinated by the pyridine nitrogen atom and the adjacent amine groups of the chain, …
First synthesis of the chiral mixed O/S ligands, 1,2-sulfinyl thiols: application as chiral proton sources in enantioselective protonations of enolat…
2000
Abstract A suitable method for the preparation of the chiral mixed O/S ligands 1,2-sulfinyl thiols is described. These compounds have then been used as a chiral proton source in the enantioselective protonation of 2-methyl tetralone enolate and the results are compared with those obtained from the analogous alcohols. A theoretical model is proposed to explain the different behaviors exhibited in the protonation reaction for each of these proton sources. Configurational assignments for the new chiral thiols have been carried out by means of X-ray analysis.
Synthesis of a new mesostructured lamellar oxovanadium phosphate assembled through an S+X-I0 Mechanism
1999
A new lamellar mesostructured oxovanadium(V) phosphate, (DDAH)0.9(Cl)0.9VOPO4·1.5H2O (DDA = dodecylamine), has been synthesized through a S+X-I0 cooperative mechanism using protonated dodecylamine ...
Adduct formed by chromium trioxide and zwitterionic quinolinic acid
2010
Abstract Chromium trioxide forms an adduct with zwitterionic quinolinic acid. The structure of the product was found to be (quinolinium-3-carboxylato-O)trioxidochromium(VI), determined by single-crystal X-ray diffraction methods. To evaluate the bonding properties of the compound, its structure was optimized at the B3LYP/6-311G* level of theory. The electronic characteristics were investigated by topological methods applied to the total charge density in various model compounds including the title compound, title compound with a HF molecule presenting a hydrogen bonding and anionic moiety. Calculated aromaticity indices indicate that the quinolinic rings tend to conserve their degree of aro…
Surface complexation modeling of arsenate adsorption by akagenéite (β-FeOOH)-dominant granular ferric hydroxide
2014
Abstract A surface complexation model has been set up for the first time with akaganeite (β-FeOOH), a major compound of granular ferric hydroxide (GFH) used in groundwater purification units worldwide for arsenic and other toxic pollutant removal. Unlike the situation for the α-FeOOH polymorph goethite, there is yet no published surface complexation model to predict competing oxyanion effects. This is due to a linked bulk-surface reactivity by which excess protons released in an unknown amount from tunnel sites hamper quantification of surface protonation by acid titration. The measured proton uptake thus exceeds what can be expected from OH groups active in surface protonation. However, ch…
Synthesis, Characterization, and X-ray Crystal Structures of Cyclam Derivatives. 5. Copper(II) Binding Studies of a Pyridine-Strapped 5,12-Dioxocycla…
2004
The copper(II) binding properties of the macrobicyclic diamide 1,9,12,18,22-pentaazatricyclo[7.6.6.1(3,7)]docosa-3,5,7(22)-triene-13,19-dione (L1) have been fully investigated by spectroscopic (IR, UV-vis, EPR, MALDI-TOF MS), X-ray diffraction, potentiometric, electrochemical, and spectroelectrochemical methods. This constrained receptor possesses a hemispherical cavity created by cross-bridging the 1 and 8 positions of trans-dioxocyclam (1,4,8,11-tetraazacyclotetradecane-5,12-dione, L2) with a 2,6-pyridyl strap. Treatment of L1 with a copper salt in methanol produces a red complex of [Cu(L1H(-1))]+ formula in which the copper atom is embedded in a 13-membered ring and coordinated by both a…
Self-Immolative Linkers as Caps for the Design of Gated Silica Mesoporous Supports
2016
A new hybrid material based on sulforhodamine-B dye-loaded silica mesoporous nanoparticles capped with a self-immolative gate has been synthesized and characterized. The gated material's controlled release behavior is monitored under different pH conditions. Under acidic and neutral conditions, a low level of dye release is detected. However, at slightly basic pH, significant dye release occurs owing to deprotonation of the phenol moiety in the capping molecule, which results in its disassembly.