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Isomeric solvates

The presence of such isomeric solvates may account for the asymmetry noted (62, 6) when carrying out the curve resolution of the 90-MHz spectra, but, within the accuracy attainable, the effect is barely significant. There are discrepancies in the values for the intrinsic shifts of the solvated species recorded by all three groups of workers (but differences between successive solvates are more satisfactory). Toma and co-workers calculated (62) the theoretically expected and isomeric differences between successive solvates, obtaining reasonable agreement with observed values (Table V). [Pg.190]

This form of isomerism, sometimes known as hydrate isomerism in the special case where water is involved, is similar in some ways to ionization isomerism. Solvate isomers differ by whether or not a solvent molecule is directly bonded to the metal ion or merely present as free solvent in the crystal lattice or solution. An example is provided by the aqua complex [Cr(H20)JCl3 and its solvate isomer [Cr(H20)5Cl]Cl2.H20. [Pg.65]

Chiral solvating agents (CSA) form diastereo-isomeric. solvation complexes with solute enantiomers via rapidly reversible equilibria in competition with the bulk solvent. [Pg.544]

Van der Zwan G and Hynes J T 1984 A simple dipole isomerization model for non-equilibrium solvation dynamics in reactions in polar solvents Chem. Phys. 90 21-35... [Pg.866]

These isomerization processes may be dependent on the nature of the solvent. For example, the rotational barrier of the tetrazathiapentalenes 15.15 (ca. 16 kcal moF ) is influenced by the donor or acceptor ability of the substituents X and Y through the S N short contacts.Solvents with acidic protons increase the magnitude of the barrier, whereas solvents that are good Lewis bases decrease the size of the barrier, owing to solvation of the transition state. [Pg.298]

Chromium, tetraaquadichloro-chloride dihydrate hydrate isomerism, 1, 183 Chromium, tetrabromo-solvated, 3, 758 synthesis, 3, 763 Chromium, tetrachloro-antiferromagnetic, 3, 761 ferromagnetic magnetic properties, 3,7559 optical properties, 3,759 structure, 3,759 solvated, 3. 758 synthesis. 3, 759 Chromium, tetrachlorooxy-tetraphenylarsenate stereochemistry, 1,44 Chromium, tetrahalo-, 3,889 Chromium, tetrakis(dioxygen)-stereochemistry, 1,94 Chromium, triamminediperoxy-structure. 1, 78 Chromium, tricyanodiperoxy-structure, 1, 78 Chromium, trifluoro-electronic spectra, 3, 757 magnetic properties, 3, 757 structures, 3, 757 synthesis, 3, 756 Chromium, trihalo-clcctronic spectra, 3, 764 magnetic properties, 3, 764 structure, 3, 764 synthesis, 3, 764 Chromium, tris(acetylacetone)-structure. 1, 65 Chromium, tris(bipyridyl)-... [Pg.101]

Cobalt, cis-chloroamminebis(l, 2-ethanediamine)-optical isomerism, 1,12 Cobalt, chlorobis(l,2-ethanediamine)-solvation, 1,503... [Pg.106]

Recently, Eisenthal and coworkers have developed time-resolved surface second harmonic techniques to probe dynamics of polar solvation and isomerization reactions occurring at liquid liquid, liquid air, and liquid solid interfaces [22]. As these experiments afford subpicosecond time resolution, they are analogous to ultrafast pump probe measurements. Specifically, they excite a dye molecule residing at the interface and follow its dynamics via the resonance enhance second harmonic signal. [Pg.408]

Furthermore, it is often possible to extract from the structural analysis of solid solvates a significant information on solvation patterns and their relation to induced structural polymorphism. An interesting illustration has been provided by crystal structure determinations of solvated 2,4-dichloro-5-carboxy-benzsulfonimide (5)35). This compound contains a large number of polar functions and potential donors and acceptors of hydrogen bonds and appears to have only a few conformational degrees of freedom associated with soft modes of torsional isomerism. It co-crystallizes with a variety of solvents in different structural forms. The observed modes of crystallization and molecular conformation of the host compound were found to be primarily dependent on the nature of the solvent environment. Thus, from protic media such as water and wet acetic acid layered structures were formed which resemble intercalation type compounds. [Pg.16]

Gas-phase ion chemistry is a broad field which has many applications and which encompasses various branches of chemistry and physics. An application that draws together many of these branches is the synthesis of molecules in interstellar clouds (Herbst). This was part of the motivation for studies on the neutralization of ions by electrons (Johnsen and Mitchell) and on isomerization in ion-neutral associations (Adams and Fisher). The results of investigations of particular aspects of ion dynamics are presented in these association studies, in studies of the intermediates of binary ion-molecule Sn2 reactions (Hase, Wang, and Peslherbe), and in those of excited states of ions and their associated neutrals (Richard, Lu, Walker, and Weisshaar). Solvation in ion-molecule reactions is discussed (Castleman) and extended to include multiply charged ions by the application of electrospray techniques (Klassen, Ho, Blades, and Kebarle). These studies also provide a wealth of information on reaction thermodynamics which is critical in determining reaction spontaneity and availability of reaction channels. More focused studies relating to the ionization process and its nature are presented in the final chapter (Harland and Vallance). [Pg.376]

Protonation and solvation in strong aqueous acids, 13, 83 Protonation sites in ambident conjugated systems, 11, 267 Pseudorotation in isomerization of pentavalent phosphorus compounds, 9, 25 Pyrolysis, gas-phase, of small-ring hydrocarbons, 4, 147... [Pg.339]

In contrast to the azaquinones 1 and 3, there is no literature report on the isomeric azaquinone 2. Reported hydroxy azaquinone 17 obtained by oxidation of 2,3,4-pyridinetriol can be considered to be its 2,3-dioxo-4-hydroxy tautomer (Scheme 5) (1883JPR257). In addition, this compound was identified only as its solvate with the alcohol of crystallization, which suggests the possibility of structure 18 instead [73AG(E)139]. [Pg.146]

The several theoretical and/or simulation methods developed for modelling the solvation phenomena can be applied to the treatment of solvent effects on chemical reactivity. A variety of systems - ranging from small molecules to very large ones, such as biomolecules [236-238], biological membranes [239] and polymers [240] -and problems - mechanism of organic reactions [25, 79, 223, 241-247], chemical reactions in supercritical fluids [216, 248-250], ultrafast spectroscopy [251-255], electrochemical processes [256, 257], proton transfer [74, 75, 231], electron transfer [76, 77, 104, 258-261], charge transfer reactions and complexes [262-264], molecular and ionic spectra and excited states [24, 265-268], solvent-induced polarizability [221, 269], reaction dynamics [28, 78, 270-276], isomerization [110, 277-279], tautomeric equilibrium [280-282], conformational changes [283], dissociation reactions [199, 200, 227], stability [284] - have been treated by these techniques. Some of these... [Pg.339]

However, the behaviour near m = raB needs some other explanation. My proposal involves the specific solvation of the backside of the carbenium ion by the strong dipole of the solvent this displaces the monomer molecule which is located there in the absence of the solvent, so that the 7t-bond to the monomer at the front is weakened and the unimolecular isomerization-propagation becomes accelerated, despite the statistical factor which, alone, would produce a deceleration, as explained at the end of Section 3a. As the dilution proceeds from m = raB downwards, the polymerization goes through a dieidic phase, in... [Pg.367]

The triplet reaction of 2-nitrodibenzo[fc,primary amines (n-propylamine and benzylamine) was studied110 in polar and apolar solvents. In polar solvents, the irradiation results in the formation of two isomeric compounds, (alky-lamino)hydroxynitrodiphenyl ether andiV-(alkylamino)-2-nitrophenoxazine (equation 54). In apolar solvents, only the nitrophenoxazine is obtained. In polar solvents, the exciplex formed between the 2-n i trodi benzol h,e [ 1,4]dioxin triplet state and amines dissociates to the solvated radical ions, from which the diphenyl ether arises. 1-Nitrodibenzo[fr,e][l,4]dioxin is stable even on prolonged irradiation. [Pg.708]

These authors conclude that the problem of internal solvation is still an experimental and theoretical challenge GB measurements for this type of molecules of low volatility are not always in good agreement194. Molecular orbital calculations may help to solve the difficult experimental problems, but they have to take into account conformational isomerisms and the prototropic tautomerisms of the amidine and guanidine moieties. In light of the above discussion, the proton affinities deduced from the experimental GB values should be based on accurate estimations of the entropy of cyclization 86. [Pg.1285]

The formation of both isomeric chlorides 147 and 148 and the corresponding methoxy adducts 149 and 150 in methanol is at variance with the behavior observed in AcOH/ LiC104, where only the acetoxy species 140 is formed. This has been interpreted by taking into account the possible role of a specifically solvated carbenium ion pair, such as 145, prior to the formation of a free carbenium ion of type 144. [Pg.617]

We have examined the competing isomerization and solvolysis reactions of 1-4-(methylphenyl)ethyl pentafluorobenzoate with two goals in mind (1) We wanted to use the increased sensitivity of modern analytical methods to extend oxygen-18 scrambling studies to mostly aqueous solutions, where we have obtained extensive data for nucleophilic substitution reactions of 1-phenylethyl derivatives. (2) We were interested in comparing the first-order rate constant for internal return of a carbocation-carboxylate anion pair with the corresponding second-order rate constant for the bimolecular combination of the same carbocation with a carboxylate anion, in order to examine the effect of aqueous solvation of free carboxylate anions on their reactivity toward addition to carbocations. [Pg.327]

With increasing concentration of methylated /1-cyclodextrin the selectivity to n-nonanal increases from 64% to 72%, while the conversion of the olefin is constantly as high as 97%. Obviously the addition of the methylated /i-cyclodextrin has only a moderate influence on the isomerizing hydroformylation of trans-4-octene to n-nonanal. The addition of only 0.2 mol.-% of methylated /3-cyclodextrin lowers the isomerization rate which results in the formation of slightly more branched aldehydes. In pharmacy j6-cyclodextrins are established as solvation mediators between polar and less polar solvents. This is one possible explanation for the rise in selectivity to n-nonanal with an increasing j6-cyclodextrin concentration. At higher con-... [Pg.36]

This interconversion can also be performed in solvents, and the rate of the isomerization is dependent on the solvent used. In the dipolar aprotic solvent DMSO the rate of the reaction is fast, but in methanol, acetone, or dioxane the rate is low. However, the value of the equilibrium constant is scarcely influenced by the solvent ( 134/133 = 6-10) (75JHC985).This is not too surprising, since the equilibrium position is controlled by the relative thermodynamic stability of the isomers, which is a function of their heats of formation and of solvation. Undoubtedly, the heat of formation is the more important factor to the thermodynamic stability (75JHC985). [Pg.201]


See other pages where Isomeric solvates is mentioned: [Pg.183]    [Pg.183]    [Pg.896]    [Pg.18]    [Pg.116]    [Pg.151]    [Pg.233]    [Pg.6]    [Pg.390]    [Pg.408]    [Pg.718]    [Pg.25]    [Pg.5]    [Pg.254]    [Pg.161]    [Pg.299]    [Pg.239]    [Pg.591]    [Pg.241]    [Pg.574]    [Pg.255]    [Pg.48]    [Pg.104]    [Pg.297]    [Pg.172]    [Pg.50]   
See also in sourсe #XX -- [ Pg.187 ]




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Solvate isomerism

Solvate isomerism

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