New Approach to Analysis of the Nonlinearity of the Brønsted Relationship: II. An Empirical Procedure Combining the σρ Correlation Method with the Concept of Hard and Soft Acids and Bases,as Applied to Pseudo CH Acids

A comparative systematic analysis of the features of Brönsted behavior of pseudo CH acids(according to Eigen's classification) is made. The analysis is based on combined use of experimental data onpK _a, Ggas, logk _D of CH acids (Ggas is the free energy of acid ionization in the gas phase, logk _D isthe logarithm of the rate constant of hydrogen exchange in a protic solvent). The modified nucleophilicKabachnik constants ^- are applicable to correlations for all the three kinds of acidity of pseudo CH acids. The electrostatic solvation makes an insignificant contribution to variation of pK _a and weakening of the substituent effect in going from the gas phase to dimethyl sulfoxide, and also to differentiation of the kinetic acidity. The coefficient in the Brönsted equation and the ratio between the rate constants in the correlations, which characterize the degree of proton transfer in the reaction transition state, have much in common from the physical viewpoint. The results of correlation analysis, demonstrating intramolecular uniformity of the interactions, are fully consistent with the conclusion made in the previous part of this work about the solvation uniformity of the interactions, resulting in the absence of thermodynamic deviations from the Brönsted relationship.     

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.     

Reactivity of N-Phenylanthranilic Acid Derivatives: XIII. Electrical Conductivity of Solutions of Substituted 4-Nitro-N-phenylanthranilic Acids in the Dioxane-Water System

Conductometry was used to determine limiting equivalent electrical conductivity (₀), Pisarzhevskii-Valden product (₀₀), hydrodynamic ionic radii, ionization constants, thermodynamic parameters for substituted 4-nitro-N-phenylanthranilic acids (7 compounds) in the system dioxane-water at varioustemperatures. It was established that the ionization is endothermic and the entropy factor is prevailing. It was found that the reaction center is moderately sensitive to substituents and the sensitivity decreases with temperature. Multifactor correlation analysis showed that the reaction constants are roughly equal to r _I and _R but are half the values for substituted benzoic acids. The reaction series studied was found to be isoentropy. Inconsiderable solvation of the anions of the substituted anthranilic acids was revealed.     

Acid-Base Properties of Substituted 9-Chloroacridines

Ionization constants (pKBH⁺) of eleven substituted 9-chloroacridines in water-ethanol mixtureswere measured by potentiometric titration at 25°C. The correlation between pKBH⁺, the Hammett constants was established, and the reaction parameter was evaluated. The sensitivity of the reaction center tothe effect of substituents is low. Annelation of the heterocycle decreases the sensitivity of the reaction center to the structural changes in the molecule.     

Radiation-induced crosslinking: II. Effect on the crystalline and amorphous densities of polyethylene

Small-angle x-ray scattering (SAXS) was used to determine the structural changes in polyethylene induced by radiation. The changes in densities of the crystalline and amorphous phases, _c and _a , were calculated after direct determination of the mean square density fluctuation <²>. _a increases with increasing radiation dose for both linear and branched polyethylene. This accounts for the serious discrepancy between crystallinities determined from wide-angle x-ray scattering and density measurements. This study confirms our previous proposal that crosslinks occur primarily in the noncrystalline phase, most likely at the defects in the lateral grain boundary regions.Dedicated to Prof. Dr. W. Pechhold on the occasion of his 60th birthday.     

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.     

The N(4S) + N2O(X̃1∑) reaction

The title reaction, which is spin‐forbidden for N₂(X¹∑) + NO(X²Π) production, has been studied from 960 to 1130 K in a high‐temperature photochemistry reactor. No reaction could be observed, indicating k < 1 × 10^?15 cm³ molecule^?1 s^?1. It is concluded that there is no significant contribution from the spin‐allowed exothermic path leading to N₂(X¹∑) + NO(a⁴Π). © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 387–389, 2001     

The Crystal Structures of Rubidium and 4-Amino-1,2,4-Triazolium Tetrafluoroantimonates(III)

The crystal structures of complex antimony(III) fluorides RbSbF₄ (I) and (C₂N₄H₅)SbF₄ (II) were determined. The crystals of I and II are monoclinic; for I: a = 4.628(1) Å, b = 6.167(1) Å, c = 7.922(1) Å, = 100.582(3)°, V = 222.24(7) ų, Z = 2, (calcd.) = 4.23 g/cm³, (exp.) = 4.25 g/cm³, F(000) = 248, space group P2₁/m, R = 0.0395; for II: a = 4.678(1) Å, b = 7.339(4) Å, c = 10.185(1) Å, = 90.88(2)°, V = 349.6(2) ų, Z = 2, (calcd.) = 2.69 g/cm³, (exp.) = 2.70 g/cm³, F(000) = 264, space group P2₁. The structure of I is formed by Rb⁺ cations and [SbF₄] ^n– _n anionic chains composed of SbF₅E octahedra with two bridging fluorine atoms. The structure of IIis formed by (C₂N₄H₅)⁺ cations and isolated [SbF₄]^– anions in which the antimony polyhedra are SbF₄E trigonal bipyramids. The relationship between the crystal structures and electrophysical and biological properties of single-charged cation tetrafluoroantimonates(III) was studied.     

On quantum-chemical estimates of constants of isotropic hyperfine coupling with protons in free radicals

A scheme of consitent quantum-chemical calculations of constants of isotropic hyperfine coupling (IHFC) with protons (a _H ^iso ) in free radicals is considered for the case where the spin populations ρ_s ^H are determined in the basic set of symmetrically orthogonalized atomic orbitals taking model σ-and π-electron fragments as an example. The competence of using two coefficients of proportionalityK(H) when estimating the proton IHFC constants by semiempirical quantum-chemical methods was demonstrated. Theoretical substantiation of empirical values of the above coefficients previously used is revealed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 245–249, February, 1999.     

Influence of Substituents on Kinetics of the Reaction of Carbonyl Oxides with Ethanol

The reactivity toward EtOH of nine carbonyl oxides (ROO) obtained by the thermolysis of the corresponding diazo compounds (RN₂) is studied by the chemiluminescence method. The reactivity is characterized by the ratio of constants k ^EtOH ₃₃/k ₃₁, where k ^EtOH ₃₃and k ₃₁are the rate constants of the reactions of ROO with EtOH and RN₂, respectively. The negative slope of the Taft correlations ( < 0) indicates the electrophilic character of the reaction of ROO with EtOH. The substituents, electron density acceptors, increase the relative reactivity of the carbonyl oxides.     

Palladium Clusters Pd4(SEt)4(OAc)4and Pd6(SEt)12: Structure and Properties

Palladium clusters Pd₄(SEt)₄(OAc)₄(I) and Pd₆(SEt)₁₂(II) were synthesized and studied. Their structure was determined by X-ray diffraction analysis. For I, a= 9.774(2) Å, b= 10.821(2) Å, c= 13.061(3) Å, = 92.88(3)°, V= 1379.6(5) ų, (calcd.) = 2.182 g/cm³, space group P2₁/n, Z= 4, N _ref= 1558, and R= 0.031; for II, a= 10.581(1) Å, b= 10.584(2) Å, c= 11.478(2) Å, = 101.62(1)°, = 104.95(1)°, = 106.74(1)°, V= 1135.2(4) ų, (calcd) = 2.007 g/cm³, space group P1, Z= 1, N _ref= 2828, and R= 0.022. In cluster I, four Pd atoms form a planar cycle. The neighboring palladium atoms are bound by two acetate or by two mercaptide bridges, the Pd···Pd distances being 3.036–3.195 Å. In cluster II, Pd atoms form a planar six-membered cycle with Pd···Pd distances of 3.083–3.127 Å. The neighboring palladium atoms are bound by two mercaptide bridges. The formation of analogous clusters in solution was confirmed by IR spectroscopy.     

Hydrodynamics and heat transfer in a plasma spouted bed reactor

The literature reveals very little intformation about plasma spouted bed hydrodynamics. Spouting of corindon particles with diameters ranging from 0.4 to 3.36 mm with argon plasma was conducted in a 90-mm-diameter column in the temperature range 300–1300°C. It was found that the maximum spoutable height (H_m) decreases with increasing particle diameter and decreasing mean bed temperature. A relation between the inlet plasma velocity and H_m is proposed. Concerning heat transport phenomena in the annulus, measurements and calculations indicate a large axial diffusivity but a poor radial mixing. Typical values of D_z and D_r are proposed on the basis of an identification procedure.Notation Ar Archimede number - Ar d ³ p (p — f) _f g ² - C_p specific heat - d_p particle diameter - d_e core diameter (or spout diameter) - D_i fluid inlet orifice diameter - D_e column diameter - D_r and D_z radial and axial diffusivity, respectively - g acceleration due to gravity - H packed static bed height - H_b bed height - H_m maximum spoutable bed height - P power     

Anwendung der Charakterordnungen auf Diels-Alder-Reaktionen bei substituierten Anthracenen

Zusammenfassung Eine lineare Abnahme der mittlerenendo-cisoiden Charakterordnungen _d mit der Geschwindigkeitskonstanten der Addition von Maleinsäureanhydrid an die 9,10-Position substituierter Anthracene wurde gefunden.

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Application of character orders to the diels-alder reactions in substituted anthracenes

A linear decrease of the meanendo-cisoidic dienoid character orders _d with the rate constants of the addition of maleic anhydride to the 9,10-position in substituted anthracenes was found.

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Mit 1 Abbildung

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HErrn Prof. Dr.Otto Hromatka zum 65. Geburtstag gewidmet.

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3. Mitt.:H. Sofer, G. Derflinger undO. E. Polansky, Mh. Chem.99, 1895 (1968).     

Synthesis and Study of Potassium Hexabromoiridate(IV)

A new method of synthesis of potassium hexabromoiridate(IV) was developed. This complex was studied using X-ray diffraction and elemental analyses and electronic absoprtion, IR, and Raman spectroscopy methods. Crystallographic parameters: a = 10.298(5) Å, V = 1092.1 ų, Z = 4, space group Fm3m, (calcd) = 4.560 g/cm³; K₂[PtCl₆] structural type. The thermal decomposition of this salt in an inert atmosphere was investigated.     

Behavior of M[Al2Me6N3] (M=K,Rb, Cs) with aromatic solvents and the crystal structures of Cs[Al2Me6N3]·2p-xylene and [K·dibenzo-18-crown-6] [Al2Me6N3]· 1.5(1-methylnaphthalene)

The title compounds were synthesized by the addition of AlMe₃ to the corresponding azide suspended in an aromatic solvent. Both products were obtained as air-sensitive colorless crystals. Cs[Al₂Me₆N₃]·2p-xylene crystallizes in the monoclinic space groupC2/m witha=19.143(6),b=16.227(6),c=10.392(5) Å, =114.06(2)^o, and _calc = 1.20 g cm^–3 forZ=4. Refinement led to a conventionalR value of 0.037 for 2179 observed reflections. The cesium atom resides on a mirror plane, and the anion is disordered about a twofold axis. Thep-xylene molecules sandwich the cesium ion.[K·dibenzo-18-crown-6] [Al_Me6N₃]·1.5(1-methylnaphthalene) crystallizes in the monoclinic space groupP2₁/c witha=14.176(5),b=13.021(5),c=25.324(8) Å, =98.23(4)⁰, and _calc = 1.08 g cm^–3 forZ=4. The finalR value was 0.132 for 1402 observed reflections. One of the 1-methylnaphthalene molecules is disordered about a center of inversion and interacts with the potassium ion. The other solvent molecule is found roughly in layers in the lattice and also exhibits disorder of the methyl substituent. For both title compounds the AlMe₃ groups of the anion exhibit a staggered (C _s) conformation. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82015 (32 pages).     

1-Aminoadamantane as guest molecule in dodecasil 1H: an X-ray crystallographic study

Dodecasil 1H, 34SiO₂ · 3M¹² · 2M¹² · 1M²⁰ with M¹², M¹²=N₂ and M²⁰=1-aminoadamantane, is hexagonal witha=13.825(2) Å,c=11.189(2) Å and crystallizes in space groupP6/mmm. With 767 unique reflexions the structure has been refined to a weighted reliability factorR _w =0.054. The three-dimensional four-connected host framework is built by corner sharing [SiO₄] tetrahedra and shows three types of cagelike voids, [5¹²] cages, [4³5⁶6³] cages and [5¹²6⁸] cages, the latter housing the 1-aminoadamantane guest molecule. Difference Fourier synthesis (obs)-(calc(Si,O)) delineate the guest molecules within the different types of cage. Residual electron densities reveal positional disorder of the 1-aminoadamantane guest molecule. Four crystallographically different preferred orientations for the 1-aminoadamantane guest molecule are found.     

Measurement of Some Thermodynamic and Acoustic Properties of Binary Solutions of N,N-Dimethylformamide with 1-Alkanols at 30°C and Comparison with Theories

Densities, and ultrasonic velocities, uof binary mixtures of N,N-dimethylformamide (DMF) + methanol, + ethanol, + 1-propanol, + 1-butanol, + 1-pentanol, and + 1-hexanol have been measured at 30°C. The ultrasonic velocities have been compared with values calculated from the free-length theory ( FLT) due to Jacobson and collision-factor theory ( CFT) due to Schaaffs. The measured data are used to compute adiabatic compressibility (k _s), deviation in adiabatic compressibility (k _s), intermolecular free length (L _f), molar volume (V _m), and available volume (V _a). The excess molar volume ( V _m ^E) and excess free length (L _f ^E) are also evaluated. For all systems, these results were satisfactorily correlated by the Redlich–Kister polynomial. These parameters are used to discuss dissociation of the self-associated 1-alkanol molecules and the formation of aggregates between unlike molecules through C=O...H–O hydrogen bonding.     

On the Interaction of Two Finite-Dimensional Quantum Systems

Interaction of quantum system S ^a described by the generalised × eigenvalue equation A| _s =E _s S ^a | _s (s=1,...,) with quantum system S ^b described by the generalised n×n eigenvalue equation B| _i = _i S ^b | _i (i=1,...,n) is considered. With the system S ^a is associated -dimensional space X ^a and with the system S ^b is associated an n-dimensional space X _n ^b that is orthogonal to X ^a . Combined system S is described by the generalised (+n)×(+n) eigenvalue equation [A+B+V]| _k = _k [S ^a +S ^b +P]| _k (k=1,...,n+) where operators V and P represent interaction between those two systems. All operators are Hermitian, while operators S ^a ,S ^b and S=S ^a +S ^b +P are, in addition, positive definite. It is shown that each eigenvalue _{k i} of the combined system is the eigenvalue of the × eigenvalue equation . Operator in this equation is expressed in terms of the eigenvalues _i of the system S ^b and in terms of matrix elements _s |V| _i and _s |P| _i where vectors | _s form a base in X ^a . Eigenstate | _k ^a of this equation is the projection of the eigenstate | _k of the combined system on the space X ^a . Projection | _k ^b of | _k on the space X _n ^b is given by | _k ^b =( _k S ^b –B)^–1(V– _k P})| _k ^a where ( _k S ^b –B)^–1 is inverse of ( _k S ^b –B) in X _n ^b . Hence, if the solution to the system S ^b is known, one can obtain all eigenvalues _{k i} } and all the corresponding eigenstates | _k of the combined system as a solution of the above × eigenvalue equation that refers to the system S ^a alone. Slightly more complicated expressions are obtained for the eigenvalues _{k i} } and the corresponding eigenstates, provided such eigenvalues and eigenstates exist.     

Pulse radiolytic reduction studies of 1,4,4a,8a-tetrahydro-endo–1,4-methano-naphtha-5,8-dione (THMND): effect of tertiary structure

Radiolytic reduction of a substituted 5,8-naptha dione (THMND), synthesized in our laboratory, has been investigated by pulse radiolysis and steady-state -radiolysis in pure aqueous, aqueous-formate and in aqueous-2-propanol-acetone mixed solvent systems. The rate constants of formation of the semi-dione radicals were approx. 10⁹ dm³ mol^-1 s^-1 in aqueous-formate and aqueous-2-propanol-acetone mixed solvent. The semi-dione radicals decay by second order kinetics with rate constants (2k) of about 10⁹ and 10⁸ dm³ mol^-1 s^-1 in the above two solvents, respectively. The pK _a value of the radical was found to be 5.0 in aqueous-formate solution and 5.8 in the aqueous-2-propanol-acetone mixed solvent. The one-electron reduction potential (E ¹) value at pH 7, determined from the pulse-radiolysis experiment, was found to be –420 ± 20 mVvs. NHE at 298 K and was independent of solvent. Ab initio calculations on its one-electron reduction reaction suggest the formation of a radical, which is different from a semiquinone where the electron density is delocalised over the two oxygen atoms. Experimental absorption maxima of the radical in aqueous solution also agree very well with the ab initio calculated values. Steady-state -radiolysis of THMND produces the corresponding two-electron reduced species.