Search results for "conformation"
showing 10 items of 1414 documents
A computational study of the lowest singlet and triplet states of neutral and dianionic 1,2-substituted icosahedral and octahedralo-carboranes
2006
This work introduces a calibrated B3LYP/6-31G(d) study on the electronic structure of singlet and triplet neutral species of 1,2-substituted icosahedral 1,2-R(2)-1,2-C(2)B(10)H(10) and octahedral 1,2-R(2)-1,2-C(2)B(4)H(4) molecules with R = {H, OH, SH, NH(2), PH(2), CH(3), SiH(3)} and their respective dianions formed by proton removal on each R group. A variety of small adiabatic singlet-triplet gaps DeltaE(ST) are obtained from these systems ranging from 2.93 eV (R = NH(2)) <or= DeltaE(ST) <or= 3.98 eV (R = SiH(3)) for the icosahedral neutrals and 1.56 eV (R = NH(2)) <or= DeltaE(ST) <or= 4.13 eV (R = SiH(3)) for the octahedral neutrals, these gaps being globally smaller for the dianionic s…
From attraction to repulsion : anion–π interactions between bromide and fluorinated phenyl groups
2011
Anion–π interactions in crystals of fluorobenzyl ammonium salts depend on the degree of fluorination at the aromatics.
Cooperativity of H-bonding and anion–π interaction in the binding of anions with neutral π-acceptors
2012
A rare anion-π complex between bromide and a neutral receptor is reported and related receptor systems are studied with a series of anions. The interaction is observed in the solid state and in solution, and further evidence for it is obtained by a computational study.
Ion mobility mass spectrometry – an efficient tool for the analysis of conformational switch of macrocyclic receptors upon anion binding
2021
Interactions between anions and synthetic macrocyclic receptors belong to the extensively explored area of research due to the particularly important functions of anions in biological and environmental sciences. Structures of anion-macrocycle complexes are closely related to their function, highlighting the importance of structural analysis of the complexes. Here, we discuss the application of ion mobility mass spectrometry (IM-MS) and theoretical calculations to the structural analysis of tetralactam macrocycles (M) with varying flexibility and structural properties, and their complexes with anions [M + X]−. Collision cross section (CCS) values obtained from both direct drift tube (DT) and…
Chiral Monofluorobenzyl Carbanions: Synthesis of Enantiopure β‐Fluorinated β‐Phenylethylamines
2011
The preparation of a stabilized monofluorobenzyl carbanion by means of a remote homochiral sulfinyl group and its completely stereoselective reactions with N-p-tolylsulfinylimines are described. The use of these reactions followed by the simultaneous removal of both chiral auxiliaries with tBuLi, which occurs without epimerization at the benzylic position, provides the quickest entry to enantiomerically pure β-fluorinated β-phenylethylamines.
CH-Directed Anion-π Interactions in the Crystals of Pentafluorobenzyl-Substituted Ammonium and Pyridinium Salts
2010
Simple pentafluorobenzyl-substituted ammonium and pyridinium salts with different anions can be easily obtained by treatment of the parent amine or pyridine with the respective pentafluorobenzyl halide. Hexafluorophosphate is introduced as the anion by salt metathesis. In the case of the ammonium salt 4, water co-crystallisation seems to suppress effective anion-pi interactions of bromide with the electron-deficient aromatic system, whereas with salts 5 and 6 such interactions are observed despite the presence of water. However, due to asymmetric hydrogen-bonding interactions with ammonium side chains, the anion of 5 is located close to the rim of the pentafluorophenyl group (eta(1) interac…
Influence of the anions on the structure and magnetic properties of a series of bis(µ-diphexono)-bridged linear trinuclear copper(II) complexes: an e…
2011
The reaction of H(2)L (N,N'-dimethyl-N,N'-bis(2-hydroxy-3-methoxy-5-methylbenzyl)-ethylenediamine) with different copper salts, in methanol and using a H(2)L/Cu = 2 : 3 molar ratio, led to four new bis(μ-diphenoxo)-bridged Cu(3) complexes of general formula [{Cu(S)(μ-L)}(2)Cu(H(2)O)(2n)]X(2) (S = CH(3)OH, n = 1 and X = BF(4)(-) for (1) or ClO(4)(-) for (2); S = Br(3)(-) anion and n = 1 without any X species for (3); S = H(2)O, n = 0 and X = NO(3)(-) for (4)). The use in the same reaction conditions of 4,4'-bipyridine (4,4'-bipy) as connector led to the chain complex [{Cu(μ-4,4'-bipy)(0.5)(μ-L)}(2)Cu(H(2)O)(2n)](ClO(4))(2)·17H(2)O (5). The structure of the centrosymmetric trinuclear unit in …
Anion Recognition by a Bioactive Diureidodecalin Anionophore: Solid-State, Solution, and Computational Studies
2018
Recent work has identified a bis-(p-nitrophenyl)ureidodecalin anion carrier as a promising candidate for biomedical applications, showing good activity for chloride transport in cells yet almost no cytotoxicity. To underpin further development of this and related compounds, a detailed structural and binding investigation is reported. Crystal structures of the transporter as five solvates confirm the diaxial positioning of urea groups while revealing a degree of conformational flexibility. Structures of complexes with Cl−, Br−, NO3 −, SO4 2− and AcO−, supported by computational studies, show how the binding site can adapt to accommodate these anions. 1H NMR binding studies revealed exception…
General Diastereoselective Synthetic Approach toward Isospongian Diterpenes. Synthesis of (−)-Marginatafuran, (−)-Marginatone, and (−)-20-Acetoxymarg…
2012
This work describes a synthetic approach to the carbocyclic skeleton of isospongian diterpenes that uses the commercially available monoterpene (S)-carvone as a C-ring synthon, which is incorporated into the tetracyclic isospongian framework via a C -> ABC -> ABCD ring annulation strategy using intramolecular Diels-Alder and ring-closing metathesis reactions. This approach has been successfully used to prepare both the title natural isospongians and several nonnatural oxygenated analogues. A preliminary evaluation of the inhibitory activity of the small collection of synthesized isospongians on the mammalian mitochondrial respiratory chain revealed that most were able to inhibit the integra…
Synthesis and conformational analysis of tetrahydroisoquinoline- and piperidine-fused 1,3,4,2-oxadiazaphosphinanes, new ring systems
2006
Abstract Through cyclization of tetrahydroisoquinoline and piperidine 1,2-hydrazino alcohols with phenylphosphonic dichloride and phenyl dichlorophosphate, P-epimeric diastereomers of 1,6,7,11b-tetrahydro-4H-1,3,4,2-oxadiazaphosphino[5,4-a]isoquinoline-3-oxides ( 13 and 14 ), 1,6,11,11a-tetrahydro-4H-1,3,4,2-oxadiazaphosphino[4,5-b]isoquinoline-3-oxides ( 15 and 16 ) and 1,6,7,8,9,9a-hexahydro-4H-pyrido[1,2-d][1,3,4,2]oxadiazaphosphinane-3-oxides ( 17 and 18 ), the first representatives of these ring systems, were prepared. NMR and X-ray diffraction studies revealed that, independently of the P-substituent and the relative configuration of the phosphorus atom, 13 , 14 , 17 and 18 could be c…