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Here we explore the effect of the nature of organic ligands in rhenium cluster complexes [Re6Q8L6]4− (where Q=S or Se, and L=benzotriazole, 1,2,3‐triazole or 1,2,4‐triazole) on the biological properties of the complexes, in particular on the cellular toxicity, cellular internalization and localization. Specifically, the study describes the synthesis and detailed characterization of the structure, luminescence and electrochemical properties of the four new Re6 clusters with 1,2,3‐ and 1,2,4‐triazoles. Biological assays of these complexes are also discussed in addition to those with benzotriazole using cervical cancer (HeLa) and immortalized human fibroblasts (CRL‐4025) as model cell lines. Our study demonstrates that the presence of hydrophobic and π‐bonding rich units such as the benzene ring in benzotriazole significantly enhances cellular internalization of rhenium clusters. These ligands facilitate binding of the clusters to DNA, which results in increased cytotoxicity of the complexes. [ABSTRACT FROM AUTHOR]

The reaction of oxime‐tethered 1,6‐enynes with a cationic gold(I) catalyst demonstrates a great potential for the synthesis of a range of heterocycles in a diastereospecific fashion. The control of the configuration of the oxime and the alkene of the enyne moiety is the key to selectively obtain dihydro‐1,2‐oxazines, isoxazolines or dihydropyrrole‐N‐oxides as single diastereoisomers. As supported by DFT calculations, these cascade reactions proceed stepwise, by the intramolecular addition of the O or N atom of the oxime onto cyclopropyl gold(I) carbene intermediates. In this study, a rare [3,3]‐sigmatropic rearrangement of nitrones is also observed. Selective cascade: A new gold(I)‐catalyzed cyclization cascade of oxime‐tethered enynes has been developed that allows for the selective preparation of dihydro‐1,2‐oxazines, dihydroisoxazoles and dihydropyrrole N‐oxides generally as single diastereomers. In addition, these last compounds may undergo a sigmatropic rearrangement to give rise to migrated dihydropyrrole N‐oxides. [ABSTRACT FROM AUTHOR]

Abstract: The data on temperature, solvent, and high hydrostatic pressure influence on the rate of the ene reactions of 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione (1) with 2‐carene (2), and β‐pinene (4) have been obtained. Ene reactions 1+2 and 1+4 have high heat effects: ∆Hr‐n (1+2) −158.4, ∆Hr‐n(1+4) −159.2 kJ mol−1, 25°C, 1,2‐dichloroethane. The comparison of the activation volume (∆V≠(1+2) −29.9 cm3 mol−1, toluene; ∆V≠(1+4) −36.0 cm3 mol−1, ethyl acetate) and reaction volume values (∆Vr‐n(1+2) −24.0 cm3 mol−1, toluene; ∆Vr‐n(1+4) −30.4 cm3 mol−1, ethyl acetate) reveals more compact cyclic transition states in comparison with the acyclic reaction products 3 and 5. In the series of nine solvents, the reaction rate of 1+2 increases 260‐fold and 1+4 increases 200‐fold, respectively, but not due to the solvent polarity. [ABSTRACT FROM AUTHOR]

Due to disorder, [K(crypt‐222)]+ CF 3 − (1) is crystallographically indistinguishable from its isomer, a 1:1 fluoroform clathrate of deprotonated [K(crypt‐222)]+, [K(crypt‐222{‐H+})]·CHF3 (2). In our preceding publications, 1 was characterized on the basis of combined X‐ray diffraction, NMR, reactivity, labeling, acid‐base, and DFT studies. Herein we report that neither incorporation of deuterium nor any other transformation of [K(crypt‐222)]+ is observed in the presence of CD3OD/CD3OK at 70 °C or CD3S(O)CD2K/(D6)DMSO at 23 °C over hours and even days. Since fluoroform is easily and quickly deprotonated under such conditions, the demonstrated greater acidity of CHF3 relative to [K(crypt‐222)]+ provides additional evidence in favor of 1 and against 2. Likewise, crystal packing analysis and DFT calculations support 1, which has now been refined in the ultimately correct space group R32. Our previously drawn conclusions regarding [K(crypt‐222)]+ CF 3 − and the existence of a ‘naked’ trifluoromethyl anion in a condensed phase remain valid. The recent alternative refinement (Becker and Müller, Chem. Eur. J. 2017, 23, 7081 – 7086) of our raw diffraction data has been improperly performed in the wrong space group to yield a non‐charge‐balanced model [K(crypt‐222)]+·CHF3, which is hereby repudiated. Becker and Müller's attempts to resolve the charge balance issue have produced models that are inadequate from the perspective of both crystallography and chemistry. [ABSTRACT FROM AUTHOR]

Kinetic parameters of the unusual [2π + 2σ + 2σ]-cycloaddition reactions of quadricyclane ( 1) with tetracyanoethylene ( 2), 4-phenyl-1,2,4-triazoline-3,5-dione ( 3), N-phenylmaleimide ( 4), and diethyl azodicarboxylate ( 5) are determined experimentally. Additionally, the enthalpies of 1 + 2 reaction in 1,4-dioxane solution (−236.6 ± 1.0 kJ mol−1) and 1 + 3 reaction in toluene (−255.0 ± 2.8 kJ mol−1) are determined calorimetrically and shown to be the largest in absolute magnitude among all known cycloaddition reactions involving these dienophiles. Solvent effect on the rate of 1 + 3 reaction in 11 solvents is studied and found to be moderate and similar to that of the conventional Diels-Alder and ene reactions. The difference in the reaction rate constants of 1 with different dienophiles can be up to 9 orders of magnitude and is mainly caused by the difference in activation enthalpies. This difference is not correlated with the standard enthalpies of reactions and is likely the result of high sensitivity of the [2π + 2σ + 2σ] reaction rates to the energy of donor-acceptor interactions between the reactants. [ABSTRACT FROM AUTHOR]

ABSTRACT The kinetics of the Diels-Alder (DA) reactions of 4-phenyl-1,2,4-triazoline-3,5-dione 1, trans-diethyl azodicarboxylate 2, and tetracyanoethene 3 with 1,3-cyclohexadiene 4, cycloheptatriene 5, 1,3-cycloheptadiene 6, cyclooctatetraene 7, and 1,3-cyclooctadiene 8 in a range of temperatures and pressures has been studied. Values of the enthalpy, entropy, and volume of activation, as well as the enthalpy and volume of reaction have been obtained. Observed reaction rates of 5+1 and 7+1 have been compared with the known rate of norcaradiene 17 formation in the equilibrium [ABSTRACT FROM AUTHOR]

[K(crypt-222)]+ [ABSTRACT FROM AUTHOR]

[K(crypt-222)]+ [ABSTRACT FROM AUTHOR]

ABSTRACT The rates of the Diels-Alder reaction of 9-(hydroxymethyl)anthracene and 9,10-bis(hydroxymethyl)anthracene with maleic anhydride and two maleimides, N-ethyl- and N-phenylmaleimide, have been studied at various temperatures and pressures in different solvent media. A rate acceleration in water in comparison with organic solvents is observed. Thermodynamic functions of activation for the reaction of 9,10-bis(hydroxymethyl)anthracene with N-ethylmaleimide in binary 1,4-dioxane-water mixtures are determined. From the observed tendencies, it can be concluded that acceleration of the Diels-Alder reactions in water is linked with an energetically favorable dehydration of the reaction centers of the reactants on the way to the activated complex. Addition of an organic cosolvent makes the desolvation of these centers less favorable. [ABSTRACT FROM AUTHOR]

First evidence for the existence of free trifluoromethyl anion CF3- has been obtained. The 3D-caged potassium cation in [K(crypt-222)]+ is inaccessible to CF3-, thus rendering it uncoordinated ("naked"). Ionic [K(crypt-222)]+ CF3- has been characterized by single-crystal X-ray diffraction, solution NMR spectroscopy, DFT calculations, and reactivity toward electrophiles. [ABSTRACT FROM AUTHOR]

ABSTRACT We have studied the solvent, temperature, and pressure influences on the reaction rates of cyclic and acyclic N=N bonds in the Diels-Alder and ene reactions. The transfer from N-phenylmaleimide ( 9) to a structural analogue, 4-phenyl-1,2,4-triazoline-3,5-dione ( 2), is accompanied by the rate increase in five to six orders of magnitude in the Diels-Alder reactions with cyclopentadiene ( 4) and 9,10-dimethylanthracene ( 5), whereas the transfer from dimethyl fumarate ( 10) to diethyl azodicarboxylate ( 1) increases only in one to two orders of magnitude. The ratio of the reaction rate constants ( 2 + 4)/( 1 + 4) is very large (5.2 × 107) and almost the same (5.3 × 107) as in the ene reactions with tetramethylethylene ( 7), ( 2 + 7)/( 1 + 7). It has been observed that the N=N bond in reagent 2 has strong electrophilic, and its N-N moiety in the transition state has nucleophilic properties, which results from the analysis of the solvation enthalpy transfer of reagents, activated complex, and adduct in the Diels-Alder reaction of 2 with anthracene 22. [ABSTRACT FROM AUTHOR]

CuCl or pre‐generated CuCF3 reacts with CF3SiMe3/KF in DMF in air to give [Cu(CF3)4]− quantitatively. [PPN]+, [Me4N]+, [Bu4N]+, [PhCH2NEt3]+, and [Ph4P]+ salts of [Cu(CF3)4]− were prepared and isolated spectroscopically and analytically pure in 82–99 % yield. X‐ray structures of the [PPN]+, [Me4N]+, [Bu4N]+, and [Ph4P]+ salts were determined. A new synthetic strategy with [Cu(CF3)4]− was demonstrated, involving the removal of one CF3− from the Cu atom in the presence of an incoming ligand. A novel CuIII complex [(bpy)Cu(CF3)3] was thus prepared and fully characterized, including by single‐crystal X‐ray diffraction. The bpy complex is highly fluxional in solution, the barrier to degenerate isomerization being only 2.3 kcal mol−1. An NPA study reveals a huge difference in the charge on the Cu atom in [Cu(CR3)4]− for R=F (+0.19) and R=H (+0.46), suggesting a higher electron density on Cu in the fluorinated complex. [ABSTRACT FROM AUTHOR]

CuCl or pre-generated CuCF3 reacts with CF3SiMe3/KF in DMF in air to give [Cu(CF3)4]− quantitatively. [PPN]+, [Me4N]+, [Bu4N]+, [PhCH2NEt3]+, and [Ph4P]+ salts of [Cu(CF3)4]− were prepared and isolated spectroscopically and analytically pure in 82-99 % yield. X-ray structures of the [PPN]+, [Me4N]+, [Bu4N]+, and [Ph4P]+ salts were determined. A new synthetic strategy with [Cu(CF3)4]− was demonstrated, involving the removal of one CF3− from the Cu atom in the presence of an incoming ligand. A novel CuIII complex [(bpy)Cu(CF3)3] was thus prepared and fully characterized, including by single-crystal X-ray diffraction. The bpy complex is highly fluxional in solution, the barrier to degenerate isomerization being only 2.3 kcal mol−1. An NPA study reveals a huge difference in the charge on the Cu atom in [Cu(CR3)4]− for R=F (+0.19) and R=H (+0.46), suggesting a higher electron density on Cu in the fluorinated complex. [ABSTRACT FROM AUTHOR]

In this study, the synthesis of new thermoactive polymer nanoparticles with a hollow and porous structure is reported. The nanoparticles consist of viologen cavitands linked with styrene bridges. The sizes of the nanoparticles and their pores are sensitive to temperature change. The temperature increase results in the swelling of the nanoparticles and in an increase in the permeability of the nanoparticle shell. The nanoparticles are characterized by the data of NMR, IR, and UV spectroscopies, and dynamic and static light scattering (DLS, SLS). The electrochemical behavior of the nanoparticles was investigated with cyclic voltammetry. The nanoparticles can be applied to the temperature-controlled binding and release of substrates as shown by the fluorescent dye rhodamine B. The nanoparticles encapsulate and release rhodamine B in response to the change in temperature from 25 to 40°C. [ABSTRACT FROM AUTHOR]

A novel class of self-assembling nanoparticles is formed with viologen-resorcin[4]arene cavitands; the association model is strongly controlled by their hydrophobicity. Interestingly, the cavitand assemblies are designed through click chemistry to form self-assembled noncovalently connected aggregates through counterion displacement. The iodide and benzoate ions are utilized as strongly polarizable counterions to induce cavitand self-assembly. The counterion- mediated decrease in hydrophilicity of the viologen-resorcin[ 4]arenes is the underlying trigger to induce particle formation. These particles can be used as nanocontainers and find their applications in delivery systems. [ABSTRACT FROM AUTHOR]

The values of the enthalpy (53.3; 51.3; 20.0 kJ mol−1), entropy (−106; −122; −144 J mol−1K−1), and volume of activation (−29.1; −31.0; −cm3 mol−1), the reaction volume (−25.0; −26.6; −cm3 mol−1) and reaction enthalpy (−155.9; −158.2; −150.2 kJ mol−1) have been obtained for the first time for the of 4-phenyl-1,2,4-triazoline-3,5-dione 1, with cyclohexene 4, 1-hexene 6, and with 2,3-dimethyl-2-butene 8, respectively. The ratio of the values of the activation volume to the reaction volume (∆ V≠corr/Δ V r − n) in the under study, 1 + 4→ 5 and 1 + 6→ 7, appeared to be the same, namely 1.16. The large negative values of the entropy and the volume of activation of studied reactions 1 + 4→ 5 and 1 + 6→ 7 better correspond to the cyclic structure of the activated complex at the stage determining the reaction rate. The equilibrium constants of these can be estimated as exceeding 1018 L mol−1, and these reactions can be considered irreversible. Copyright © 2014 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Promising membrane transport and separation systems for selected dicarboxylic, α-hydroxy- and α-amino acids based on thiacalixarene platform have been developed. For the first time, p-tert-butyl thiacalix[4]arenes functionalized at the lower rim with aminophosphonate fragments have been obtained and characterized. As was established by UV-vis spectroscopy, membrane extraction and HPLC, the substitution of amino groups by α-aminophosphonate units significantly enhances the selectivity of host molecules that bind to aspartic and glycolic acids. The aminophosphonate compounds synthesized can be used in the development of sensors and systems employed in the purification and separation of organic acids. Copyright © 2013 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Zuschauer oder Hauptdarsteller? Das Alkalimetall ‐ Gegenion (K+) spielt eine bemerkenswerte Schlüsselrolle in der kürzlich entdeckten Cuprierung von Fluoroform mit Dialkoxycuprat. Insgesamt acht synergistisch wechselwirkende Lewis ‐ Säure ‐ und Lewis ‐ Base ‐ Zentren ordnen sich zu einem stabilen Übergangszustand, wodurch der niederenergetische Reaktionsweg dieser Umwandlung bedingt wird. [ABSTRACT FROM AUTHOR]

Just a spectator or a key player? The alkali‐metal counterion (K+) plays a remarkable key role in the recently discovered cupration reaction of fluoroform with dialkoxycuprates. A total of eight Lewis acid and Lewis base centers synergistically interacting with one another arrange in a stable transition state, providing a low‐energy pathway for this unique transformation. [ABSTRACT FROM AUTHOR]

Zuschauer oder Hauptdarsteller? Das Alkalimetall ‐ Gegenion (K+) spielt eine bemerkenswerte Schlüsselrolle in der kürzlich entdeckten Cuprierung von Fluoroform mit Dialkoxycuprat. Insgesamt acht synergistisch wechselwirkende Lewis ‐ Säure ‐ und Lewis ‐ Base ‐ Zentren ordnen sich zu einem stabilen Übergangszustand, wodurch der niederenergetische Reaktionsweg dieser Umwandlung bedingt wird. [ABSTRACT FROM AUTHOR]

Just a spectator or a key player? The alkali‐metal counterion (K+) plays a remarkable key role in the recently discovered cupration reaction of fluoroform with dialkoxycuprates. A total of eight Lewis acid and Lewis base centers synergistically interacting with one another arrange in a stable transition state, providing a low‐energy pathway for this unique transformation. [ABSTRACT FROM AUTHOR]

According to the quantum chemical calculations and Dynamic NMR experiments in the distally disubstituted classical and thiacalix[4]arenes (CCA and TCA) in addition to the C2v symmetrical pinched cone (PC) conformation, the distorted cone (DC) form with an approximate Cs overall symmetry (with two OH groups bonded to one oxygen atom) also corresponds to the energy minimum. Moreover, in DC form, two different mutual orientations of O-R groups at a lower rim lead to two stable conformations: the first - with both these groups directed outward, the second - with both these groups pointing toward the same direction. In CCA, the PC is essentially favoured over the DC, while in TCA, energies of these forms are similar or the latter may be even preferable. Copyright © 2013 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Replacement of the naphthalene ligand in ruthenium complex [CpRu(C10H8)]+ ( 1) by halide anions readily proceeds at room temperature to give insoluble oligomeric species [CpRuX] n (X = Cl, Br, I). Similar reactions in the presence of mono- or bidentate ligands afford complexes [CpRuL2X] where L = CO, P(OMe)3, tBuNC; L2 = dppm, dppe, dppp, bipy, phen, cod, nbd, or 1,4-diphenylbutadiene. Useful catalysts [CpRu(cod)X] were obtained by this method in 70-90 % yields. The structure of [CpRu(cod)I] was determined by X-ray diffraction. Reaction of 1 with Br- and allyl bromide afforded RuIV complex [CpRu(η3-C3H5)]Br2. Cation 1 also was found to react with azide anion in the presence of bidentate phosphanes to afford [CpRuL2N3] (L2 = dppm, dppe). Reaction of 1 with neutral ligands in the absence of nucleophilic anions proceeded under visible-light irradiation to give cationic complexes [CpRuL3]+ [L = CO, P(OMe)3, P(OEt)3, tBuNC] in 80-90 % yields. Complex 1 (2 mol-%) catalyzed cyclotrimerization of dipropargyl Meldrum's acid with various alkynes RC≡CH [R = H, Bu, Hex, Ph, SiMe3, (CH2)4C≡CH, (CH2)3OH, (CH2)2Br, CH2OMe, CH2OAc, CH2NMeBoc] producing benzene derivatives in 50-85 % yields. According to DFT calculations, the attack of the first ligand (Cl- or L) is a rate-determining step in the naphthalene replacement in 1. The activation barrier for attack of the Cl- anion is ca. 10 kcal mol-1 lower in energy than that of the neutral ligands L = CO, MeNC, MeCN, thus providing a rationale for the faster reaction in the presence of halide anions. The barriers for naphthalene replacement in 1 were also found to be ca. 10-15 kcal mol-1 lower in energy than those for the benzene replacement in [CpRu(C6H6)]+. [ABSTRACT FROM AUTHOR]

Solvent, temperature, and high pressure influence on the rate constant of homo-Diels-Alder cycloaddition reactions of the very active hetero-dienophile, 4-phenyl-1,2,4-triazolin-3,5-dione (1), with the very inactive unconjugated diene, bicyclo[2,2,1]hepta-2,5-diene (2), and of 1 with some substituted anthracenes have been studied. The rate constants change amounts to about seven orders of magnitude: from 3.95.10−3 for reaction (1+2) to 12200 L mol−1 s−1 for reaction of 1 with 9,10-dimethylanthracene (4e) in toluene solution at 298 K. A comparison of the reactivity (ln k2) and the heat of reactions (∆ r-n H) of maleic anhydride, tetracyanoethylene and of 1 with several dienes has been performed. The heat of reaction (1+2) is −218 ± 2 kJ mol−1, of 1 with 9,10-dimethylanthracene −117.8 ± 0.7 kJ mol−1, and of 1 with 9,10-dimethoxyanthracene −91.6 ±0.2 kJ mol−1. From these data, it follows that the exothermicity of reaction (1+2) is higher than that with 1,3-butadiene. However, the heat of reaction of 9,10-dimethylanthracene with 1 (−117.8 kJ mol−1) is nearly the same as that found for the reaction with the structural C=C counterpart, N-phenylmaleimide (−117.0 kJ mol−1). Since the energy of the N=N bond is considerably lower (418 kJ/bond) than that of the C=C bond (611 kJ/bond), it was proposed that this difference in the bond energy can generate a lower barrier of activation in the Diels-Alder cycloaddition reaction with 1. Linear correlation ( R = 0.94) of the solvent effect on the rate constants of reaction (1+2) and on the heat of solution of 1 has been observed. The ratio of the volume of activation (∆ V≠) and the volume of reaction (∆ V r-n) of the homo-Diels-Alder reaction (1+2) is considered as 'normal': ∆ V≠/∆ V r-n = −25.1/−30.95 = 0.81. Copyright © 2012 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The shape of supramolecular aggregates based on stereoisomers of p-tert-butyl thiacalix[4]arenes functionaiized with secondary, tertiary amide and hydrazide groups at the lower rim in cone, partial cone and 1,3-alternate conformations with several metal cations were investigated by atomic force microscopy. The examined p-tert-butyl thiacalix[4]arenes form host-guest complexes; dimers, spherics ellipsoids and elongated nanoscale particles depending on the conformation of macrocycles, the nature of the binding centers and the nature of the metal cation. Only associates formed by p-tert-butyl thiacalix[4]arenes with morpholide groups at the lower rim in cone conformation with silver cations exhibited a higher antimicrobial activity. [ABSTRACT FROM AUTHOR]

Solvent, salt and high pressure effects on the rate and equilibrium constants for the formation of tri- n-butylphosphoniumdithiocarboxylate at 298.2 K are reported. This equilibrium is shifted to the phosphobetaine in polar solvents, salt solutions and under high external pressure. The reaction volume changes dramatically on going from less polar diethyl ether (−69 cm mol) and tetrahydrofurane (THF) (−66 cm mol), to more polar acetonitrile (−39 cm mol) and acetone (−38 cm mol). Copyright © 2010 John Wiley & Sons, Ltd. The equilibrium for the formation of tri- n-butylphosphoniumdithiocarboxylate is shifted to the phosphobetaine in polar solvents, salt solutions and under high external pressure. The pressure effect on this equilibrium results in extremely negative reaction volumes, which change sharply on going from acetone (−38) and acetonitrile (−39) to the less polar THF(−66) and diethyl ether(−69 cm mol). [ABSTRACT FROM AUTHOR]

For magnesium perchlorate (MP), the solvent effect on the heat of solution and partial molar volumes (PMV) at 25 °C was studied. Since the complete dissociation of magnesium perchlorate is more difficult to achieve as compared with lithium perchlorate (LP), the concentration dependence of the values of the heat of solution and partial molar volume were noted. Only in highly polar solvents with large donor numbers (DN), such as water, dimethyl sulfoxide, N, N-dimethyl formamide, and formamide, the differential and integral values of the enthalpies of solution were the same in the range of concentrations studied. In all solvents studied, the values of the heat of solution of MP were highly exothermic and exceed that of LP by more than 30 kcal mol. The values of the partial molar volume of MP were changed from 82.3 cm mol in formamide to −2.4 cm mol in acetone, and correlate linearly with that of LP ( R = 0.975). Taking into account the significant change in the properties of molecules in the solvate shell of cation Mg, the large increase in the reactivity of reactants, activated by such interaction with Mg cation is expected. Copyright © 2010 John Wiley & Sons, Ltd. For magnesium perchlorate the solvent effect on the heat of solution and partial molar volumes at 25°C was studied. Only in highly polar solvents with the large values of donor number, as water, dimethyl sulfoxide, N,N-dimethyl formamide, formamide, the differential and integral values of the enthalpies of solution were the same in studied range of concentrations. Very different solvent influence on the values of the heat of solution and partial molar volumes of magnesium perchlorate was observed (R=−0.02). [ABSTRACT FROM AUTHOR]

The internal and external key factors influencing the reaction rates were considered for the Diels–Alder reaction (DAR) with normal electron demand. A simple dependence lgk2 = -28.81 +316.3/(IPD-EA)-69.9 R1–4/(IPD-EA)-0.054ΔHr-n for the reaction rate as a function of the ionization potential of π-donor dienes, electron affinity of π–acceptor dienophiles, heat of reaction and diene structure (R1–4) was obtained. This relation allows one to explain the origin of the conventional and ‘anomalous’ relations between activity and selectivity, and the variety of relationships between the kinetic activity and thermodynamic stability. It helps one to choose the conditions for the directed synthesis of desired products, to explain the acceleration effects in the presence of Lewis acids and to predict the rates of the DAR between the different reagents with C&dbond;C bonds not explored earlier. Copyright © 2009 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

For several non-electrolytes and for lithium perchlorate the solvent effect on the heat of solution and partial molar volumes was studied. In the absence of the donor–acceptor and electrostatic interactions, clear proportionality can be seen only in the alkane solutions and these changes are defined by the non-alkane component. For solutions of π-acceptor (tetracyanoethylene) and ν-acceptor (gallium chloride) in the presence of π,π-, π,ν- and n,ν-complexes, the relation between the changes of interaction energy and the values of the partial molar volumes can be seen. The maximum change in the value of partial molar volumes (up to 50 cm3 mol-1) was noted for lithium perchlorate in ten solvents. The volume change is proportional to the compressibility coefficients of the solvents and correlates less with the values of heat of solution and solvent permittivity. Copyright © 2006 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Review: 65 refs. [ABSTRACT FROM AUTHOR]