Acid — Base properties of 3(5)-azido-1,2,4-triazoles

The pK_a and values of a series of 3(5)-azido-1,2,4-triazoles are correlated with the _I and _C constants according to the equation pK =_II + _CC + pK_o. The high _I values in both cases are due to the closeness of the substituent to the reaction center. The _C/_I ratio attests to different contributions of the inductive and mesomeric effects of a substituent during transmission of its effect from the 5-position to the N₁ and N₄ heteroatoms.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1288–1291, September, 1974.     

Intensity of the η(C≡C) Bands in the IR Spectra of Acetylene Derivatives and σR 0 Constants of Organosilicon,Organogermanium, and Organotin Substituents

The integral absorptivities of shape-characteristic (CC) bands in the IR spectra of 66 acetylene derivatives RCCX (R = H, Me₃M; X are inorganic and organic substituents) are related by a common linear equation to the _R ⁰ constants of the R and X substituents. The _R R⁰ constants of 10 Alk₃M substituents were calculated. The _R ⁰, _R , and _R ⁺ constants of Me₃M substituents were analyzed. The positive _R ⁰ values (0.12, 0.06, and 0.04 for R = Si, Ge, and Sn, respectively) suggest that in the ground electronic state of Me₃MCCX molecules the resonance acceptor effect of the Me₃M substituents (d, conjugation) prevails over donor (, conjugation). The first effect attenuates and the second enhances as the atomic number of M increases.     

Regression Analysis for the Host–Guest Interaction of β-Cyclodextrin with Mono- and 1,4-Disubstituted Benzenes

A multiple regression model was generated, which can satisfactorily estimate the association constants (K _a ) for the inclusion complexation of -cyclodextrin with mono- and 1,4-disubstituted benzenes. It was found that lnK K _a was correlated with the substituent molar refraction (R _m ), hydrophobic constant () and Hammett constant ) of the guest compounds with a correlation coefficient of 0.95. The main driving forces for -cyclodextrin complexation was concluded to consist of van der Waals forces and hydrophobic interactions, while the influence of electronic effects was small.     

The nature of the inductive effect of azinyl groups

The induction constants of azinyl groups are factored into two components, a -induction ( _X ) and a field (_F) component. It is shown that the _X constants of azinyl groups can be thought of as sums of contributions from the phenyl group and the endocyclic nitrogen atoms. A satisfactory correlation is found between the _F constants and the size and direction of the dipole moment of the heterocyclic substituents in the framework of the Kirkwood-Westheimer equation.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 672–676, May, 1987.     

The phenomenon of conglomerate crystallization. XX. Spontaneous resolution in coordination compounds. XVIII.

The title compound, [cis-Co(en)₂(NO₂)₂](NO₂) (1), crystallizes in the polar, nonenantiomorphic, monoclinic space group, Cc, with lattice constants:a=9.198(2) Å,b=12.444(2),c=9.963(3), and=96.76(2)°;V=1132.39 ų andd(calc;Z=4) =1.860 g cm^–3. Thus, with NO_2– as the counteranion, [cis-Co(en)₂(NO₂)₂] crystallizes in a heterochiral lattice containing racemic pairs of cations. A total of 2699 data were collected over the range of 4°270°; of these, 1859 (independent and withI3(I)) were used in the structural analysis. Data were corrected for absorption (=15.465 cm^–1) and the relative transmission coefficients ranged from 0.9934 to 0.7112. Refinement was carried out for both lattice polarities and the finalR(F) andR _w (F) residuals were, respectively, 0.0242 and 0.0202 for (–––) and 0.0264 and 0.0243 for (+++). Thus, the former was selected as correct for our specimen.Unlike all previous X-ray diffraction studies of the structural properties of the cation [cis-Co(en)₂(NO₂)₂]⁺, which are found to have a pair of oppositely configured en rings [i.e., () or ()], we find that in1 the cations are in the lowest energy conformation and configuration; i.e., () or (). We attribute this change in configuration to the formation of strong interionic hydrogen bonds between nitrite anion oxygens and the axial—NH₂ hydrogens, which markedly weaken the intermolecular and intramolecular hydrogen bonds between ligand—NO₂ oxygens and the hydrogens of those same amine moieties. Thus, the nitrite anions behave exactly as nitrate anions, except that the hydrogen bonds found here are stronger than those formed by the latter. This is as expected since the negative charge is delocalized over two, instead of three, oxygens.     

Autocatalytic oxidation of Fe(Phen)3 2+ by bromate in water-in-oil reverse micelles of AOT

Autocatalytic oxidation of ferroin by bromate in water-in-oil reverse micelles of AOT has been studied experimentally and theoretically. The simplest models for this process have been constructed. Analytical solutions for these models were found for some limiting cases. It has been shown that the autocatalytic reaction runs much more slowly in reverse micelles than in water. The dependencies of the maximum reaction rate, _max, the exponent of the increase in ferriin concentration, , and induction period, , on micelle concentration have been obtained at =[H₂O]/[AOT]=4.6. It was found that there is only one theoretical model which can explain the experimental data. The values of the elementary reaction rate constantsk _i were estimated on the basis of the theoretical dependencies of _max and on the constantsk _i . All elementary rate constants turned out to be two or three orders of magnitude smaller than the corresponding constants for the reaction proceeding in water. The decrease in the rate constants is explained by the increase in viscosity and pH in a micellar water core at low .Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1401–1407, August, 1993.This work was supported by the Russian Foundation for Fundamental Investigations through Research Grant 93-03-4090.     

Entropy in dissimilarity and chirality measures

Within the prospect of quantifying the geometrical dissimilarity of molecular models on the basis of a thermodynamical formalism, the algebra of stereogenic pairing equilibria is reviewed and applied to molecular geometry: developing Rassat's proposition, an interaction energy of two figures F and F is taken as proportional tod _H ^Emphasis>/2 (F, F), whered _H denotes the Hausdorff distance. IfG is a group of rotations in E _n the geometrical version of the general equation (E) of the chemical algebra defines a distance extensionD _p(F,F) ofd _H(F,F), which is independent of the orientations of F and F, and where the coefficientp is interpreted as the reciprocal of a temperature-like parameter:p 1/T. At K (p = ), no formal entropy contributes to the definition of the uniform distanceD . At K (p = 0), the discrimination between homo- and hetero-pairing of figures by the harmonic distance Do is averaged over orientation states. Temperature-dependent chirality measuresc _p are derived fromD _p, andc is analogous to Mislow's chirality measure. If T and oT are normalized enantiomorphic triangles with coincident centroids inE ₂,c _p(T) =D _p (T, T) is calculated forp = 0 andp = , and discussed for 0 <p < . Finally, the Hausdorff interaction model is putatively related to energy profiles versus dihedral angle inmeso- anddl-molecules.     

ESR study on the stability of W/O gel-emulsions

W/O gel-emulsions (high-internal-phase-volume-ratio emulsions) form in water (or brine) /tetraethyleneglycol dodecyl ether/heptane system above the HLB (hydrophile-lipophile balance) temperature of the system. A salt, which largely decreases cloud temperature in a water-nonionic surfactant system, makes the surfactant film rigid and the gel-emulsions hence become very stable. The effect of aded salt on the apparent order parameter S, and the isotropic hyperfine splitting constant a _N in gel-emulsions was determined by the ESR spin probe method using 5-doxyl stearic acid as the spin probe. The apparent order parameter S, and the isotropic hyperfine splitting constant a _N increase with increasing salinity in Na₂SO₄, CaCl₂, and NaCl systems. It is considered that the surfactant molecules are tightly packed in these systems and this tendency is highly related to the stability of gel-emulsions. The salt dehydrates the hydrophilic moiety of surfactant and hence the lateral interactions of surfactant molecular layer at the water-oil interface increases.The observed difference in the apparent order parameter between the ordinary emulsions and the gel-emulsions suggests that most of the surfactant molecules are adsorbed at the oil-water interface (the surface of the water droplet) in gel-emulsions.     

Contribution to the systematics of r0-derived molecular structure determinations from rotational parameters

This work investigates and enumerates the types of molecular structure that can, in principle, be obtained when moments of inertia, planar moments, or rotational constants or different forms of their isotopic differences are least-squares fitted to the respective experimental ground state values. Ther ₀-structure, ther ₀-derived pseudo-Kraitchman structuresr _I andr _B, and an inequality relation between them are discussed. A least-squares treatment that tries to determine not only the set of structural parameters but also constant, i.e., isotope-independent, rovibrational contributions to the moments of inertia or rotational constants is possible and merits preference. It is shown that the resulting structures are, however, identical with the formerr orr _B-structures, respectively.     

Copper(I) Complexes with N-allylazomethines. The Role of π- and σ-Coordination in Structure Formation of 2CuBr·R–CH=N–C3H5 (R = 2-furyl) and CuBr·R–CH=N–C3H5 (R = phenyl)

Crystals of the complexes 2CuBr·C₄H₃(O)–CH=N–CH₂–CH=CH₂ (I) and CuBr·C₆H₅–CH=N–CH₂–CH=CH₂ (II) were obtained from an ethanol solution of CuBr₂ and N-allyl-2-furylaldimine or N-allylbenzaldimine using the alternating current electrochemical procedure. Their crystal structures were determined (DARCH diffractometer, MoK radiation, 1001 (F 2 F) and 911 (F 6 F) reflections; R = 0.029 and 0.063, respectively, for I and II. , -Complex I crystallizes in space group A2/a, a = 13.698(6), b = 17.679(5), c = 10.247(4) , = 114.03(3)°, Z = 8. Crystal data for -complex II: space group P2 ₁ /a, a = 19.016(5), b = 13.876(2), c = 4.0272(9) , = 92.90(2)°, Z = 4. The structure of I involves separate - and -coordinations of copper(I) in the form of planar trigons similar to those in the analogous nonisostructural -complex with copper(I) chloride. The length of the coordinated C=C bond is 1.35(1) . The structure of II consists of infinite (CuBr) _n chains -coordinated to the nitrogen atom of the ligand molecules. The noncoordinated allyl group is disordered.     

Substituent dependence of the d-d transition band in the electronic absorption spectra of arylferrocenes and the corresponding arylferricenium salts

The electronic absorption spectra of 22 arylferrocenes and their arylferricenium salts with pentacyanopropenide (PCNP) were recorded. The attemptedHammett correlation of _max of the d-d transition bands of arylferrocenes revealed that this band is substituent dependent only for strong electron-withdrawing substituents. Excellent correlation of _max of the d-d transition bands with ⁺ constants was found in the case of arylferricenium cations. Good correlations of _max was also found with theE _1/2 oxidation potentials measured by cyclic voltametry.

---

Substituentenabhängigkeit des d-d-Überganges in den Elektronenabsorptions-Spektren von Arylferrocenen und entsprechenden Arylferricenium-Salzen

Zusammenfassung Elektronenabsorptions-Spektren von 22 Arylferrocenen und ihren Arylferricenium-Pentacyanopropenid-Salzen wurden gemessen. VersuchteHammett-Korrelationen des längstwelligen d-d-Überganges (_max) zeigten, daß diese Bande nur von stark elektronenanziehende Substituenten abhängig ist. Im Fall der Arylferricenium-Kationen wurde eine ausgezeichnete Korrelation zwischen _max der d-d-Bande und den ⁺-Konstanten festgestellt. Eine gute Korrelation der _max-Werte wurde auch mit denE _1/2 Oxidationspotentialen gefunden, die durch cyclische Voltametrie meßbar sind.

     

Predissociation lifetime of the 1σ g 2 2σ g diabatic state of He 2 + : a one-channel approach

Summary This work is concerned with the application of a one-channel model to obtaining predissociation lifetimes and transition rates in a system of crossing diabatic states. The calculation focuses on the first shape resonance of the 1 _g ² 2 _g diabatic state of He ₂ ⁺ , which is relatively stable with respect to tunneling. This resonance predissociates as a result of the 1 _g ² 2 _g state being crossed by the 1 _g 1 _u ² dissociative diabatic state near the resonance level. We have estimated its predissociation lifetime to be of the order of 10^–11 s.     

Interpreting magic-number and evaporation effects in cluster size distributions

The Smoluchowski equations describe the coalescence of clusters to form larger clusters. If the kernels or rate constants in these equations are homogeneous, meaning thatK _{j, k} = ² K _jk (wherej andk are cluster sizes), it can be shown that the populationsn _k approachAk ^a e - ^bk for largek and large time, where the constantsa andb depend on the homogeneity parameter. Deviations of observed populations from this formula may be ascribed to magic-number and/or evaporation effects on the kernels. By integrating the Smoluchowski equations numerically for various choices of the kernels, we derive population distributions and show the effects of magic-number clusters and evaporation on the population distribution. Various methods are used to extract the value of, in order to determine the best way to extract the underlying value of from experimental data. Experimental populations for sodium metal clusters are then analyzed according to the same procedure, to extract the homogeneity parameter and explain the patterns in the population distribution.     

Reactivity of N-Arenesulfonyl-ε-aminocaproic Acids

N-Arenesulfonyl--aminocaproic acids behave in aqueous dioxane as weak dibasic acids; their ionization constants were determined. The correlation of pK _a with Hammett constants was revealed, and the reaction parameters were evaluated. The reaction centers (carboxy and amide groups) are weakly sensitive to the effect of substituents in the benzene rings. Formation of an intramolecular hydrogen bond in the molecules of these acids was proved.     

Quasi-tautomerism of 5-hydroxy-5-phenyl-5H-pyrido[2,3-b]chromenes in sulfuric acid

The existence of a quasi-tautomeric equilibrium in solutions of 5-hydroxy-5-phenyl-5H-pyrido[2,3-b]chromenes in sulfuric acid, which was confirmed by a linear dependence of the logarithms of the indicator ratios on acidity function H_R — H_O with a slope close to unity, was established. The pK values of this equilibrium correlate with the _p ^o and _R. ^o substituent constants.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 753–755, June, 1984.     

Organotitanium chemistry 12. Synthesis of some new chiral cyclopentadienyl titanium and zirconium complex. The crystal structure of (S-cyclo-C4H7OCH2Cp)2TiCl2

Summary New chiral cyclopentadienyl-titanium and-zirconium complexes Cp₂TiCl₂, CpCpTiCl₂ and Cp₂ZrCl₂ (Cp=⁵ -cyclopentadienyl and Cp=substituted cyclopentadienyl), have been synthesized. The (S,S)-3 complex, which forms red plate crystals, has been studied by x-ray analysis. It belongs to the monoclinic space groupC2, witha 23.963(3),b 6.6470(6),c 12.6618(9) Å, 103.089(7)°, V=1964.4(3) ų and Z=4. The structure was relined to an R factor of 0.048 for 868 observed reflections.     

Investigation of furan acetal compounds

New 1,3-dioxanes, which are derivatives of 2-nitro-2-ethylpropane-1,3-diol and aldehydes of the furan series, were synthesized. The nitrodioxanes were reduced by means of sodium amalgam to the corresponding amines. The kinetics of the formation of the nitrodioxanes was studied. The accelerating action of the electron-acceptor diol substituent on the reaction rate was established. The rate constants in the aldehyde series increase on passing from-methylfurfural to-nitrofurfural, and they correlate satisfactorily with Brown's _p ⁺ constants.See [1] for communication IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1159–1162, September, 1972     

CH Acidity of Di- and Trisubstituted Methanes

It is shown that the CH acidity of di- and trisubstituted methanes can be studied using the ap- proaches consisting in singling out the contributions of physically significant factors from the overall acidification mechanisms in the gas phase and in solution. This procedure implies formal decomposition of the calculated gas-phase deprotonation energy Edeprot into the following terms: electrostatic energy of proton detachment from the acid CH bond, with the state of the remainder of the molecule absolutely unperturbed (E ₁); electronic relaxation energy of the resulting molecular residue and formation of a virtual carbanion therefrom (E ₂); the Edeprot component due to displacement of the atomic nuclei on changing from the virtual to real carbanion E ₃. Relationships between the energy components E ₁, E ₂, E ₃, and the commonly used characteristics of the molecular structure were investigated. The parameter E ₁ is selectively sensitive to the inductive effect of the substituent. Imperfect correlation between E ₁ and the sum of the _I constants can be due to the fact that the contributions to the _I constants from the effective charge on the hydrogen atom of the CH bond being deprotonated and from the polarizabilities of the substituents are not taken into account. In contrast to monosubstituted methanes, in di- and trisubstituted methanes there is no correlation between the E ₂ component and the ¹ J(^13CH) constants. The linear dependence linking the sums of the components E ₁ + E ₂ and the pyramidal angle in the carbanions is responsible for the relaxation nature of the effects associated with the E ₂ + E ₃ sum. Comparison of the data obtained with the calculated patterns of redistribution of the effective charges on atoms accompanying conversion of CH acids to carbanions enabled elucidation of the relative contribution of each of the components, E ₂ and E ₃, to the deprotonation energy of selected groups of substituted methanes. The previously developed technique of separating the energy of protolytic equilibrium in the gas from that of solvation processes in solution enabled assessment of the contributions from electrostatic solvation to pK _a in DMSO. The same technique of singling out the solvation component due to intermolecular hydrogen bonds from pK _a(H₂O) was used in studying the acid-base equilibria for substituted methanes in aqueous solution. It was shown that the solvation effects manifested in the liquid-phase CH acidity can be modeled by the effects revealed for analogous hydrogen bonds of ion-molecule complexes in the gas phase. The relationships between the strength of hydrogen bonds and the CH-acidic properties of compounds in the gas phase and liquid water are similar.     

INDO Calculation of Spin Densities in Radical Cations of a Series of Substituted Nitro- and m-Dinitrobenzenes

The spin densities in radical cations of 22 substituted nitro- and m-dinitrobenzenes were calculated by the INDO method. For radical anions of substituted nitrobenzenes, a good linear correlation was obtained between the spin densities s_Ns_N and experimental hyperfine coupling constants with the nitrogen atoms of the NO₂ groups (a ^N): a ^N = K _N s _N s _N, where K _N = 428.58 (R ² = 0.96). For radical anions of substi- tuted m-dinitrobenzenes, no satisfactory agreement between the calculated and experimental a ^N constants was attained.     

A tetrahedral copper(I) compound of pyrazole-substituted ethylene diamine. The crystal structure of [(N,N,N′,N′-tetrakis(pyrazol-1′-ylmethyl)-(1,2-diaminoethane)copper(I)](tetrafluoroborate) (acetonitrile)

Summary Reaction of the ligandN,N,N,N-tetrakis(pyrazol-l-yhnethyl)-1,2-diaminoethane (edtp) with Cu(MeCN)(BF₄) produces the white crystalline solid [Cu(edtp)](BF₄)(MeCN). The single-crystal x-ray diffraction showed chains of copper(I) ions linked to one another by edtp molecules. The copper ions are coordinated by four pyrazole nitrogens in an almost tetrahedral arrangement. The acetonitrile molecule and the tetrafluoroborate anion are not bound to the copper(I) ion. Crystal data: Orthorhombic space group Ima2,a=17.872(7),b=11.305(2),c=12.931(4) Å, Z=4, with R=0.038 (R_w = 0.46) for 1060 reflections with I > 2(I).