Hyperconjugation of unsymmetrical groups

The interaction of the -bond system with the -electron system in molecules of type {ie427-01} is easily determined for the symmetrical CH₃ group by isolating the -component from the system of three -bonds; CH₃ is thus treated as a C=X quasivinyl group. The theory is extended to unsymmetrical groups.Read at the Symposium on Quantum Chemistry, Palanga, June 1965.     

Calculation of the mass transfer coefficient with a chemical reaction in a gas-liquid system

A solution of the problem of mass transfer in a turbulent boundary layer has been obtained with a first-order chemical reaction occurring in the liquid phase. The dependence of the enhancement factor for absorption and of the mass transfer coefficient on the model parameters can be used for building up a hierarchic model of the gas-liquid reactor.

---

. .

     

Studies on the complexes of 4′-substituted benzo-15-crown-5 ligands with sodium picrate and picric acid

Complexes of nine 4'-substituted benzo-15-crown-5 ligands with sodium picrate were prepared. A good linear relationship of the . values from the UV spectra and Hammett [_p - _m] values was observed. Charge transfer complexes of ten 4'-substituted benzo-l5-crown-5 ligands with picric acid were isolated in crystalline form. The color of the complexes depended on the nature of the substituents. All of the complexes were identified by elemental analyses, UV and IR spectra.     

Ferromagnetism of Two-Bridge Clusters

A generalized model of angular overlapping was used to analyze the magnetic properties of polynuclear complexes. The structural elements of these complexes contain planar binuclear fragments of the M(LR)₂M type. The maximum ferromagnetism for the monoatomic bridges corresponds to = MLM, which is about 100°. Weak planar interactions between L and R displace the ferromagnetism maximum towards lower , while interactions shift it towards higher . In almost all cases, strong planar interactions (LLR 180°) are responsible for strong antiferromagnetism.     

dπ-pπ interaction in bonds of silicon with nitrogen and phosphorus

Conclusions The stretching vibration frequencies of the Si-H bond in substituted silanes containing an Si-N bond depend both on the inductive effect of the substituents and the d-p, p,- and , -conjugation effects.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2609–2611, November, 1970.     

New notions of active surface composition of reforming catalysts

Some peculiarities of adsorption and catalytic properties of electron deficient platinum atoms (Pt) in reforming catalysts are presented. It appears possible to improve catalysts modifying Pt centers with -donor molecules.     

Calculation of σ→π* and π→σ* transitions in vinylboranes

Calculations are presented of the energies of the ground and excited and electronic states of ethylene and substituted vinylboranes. The Pople-Segal-Santry method was employed throughout. It is concluded that the excited state of lowest energy in ethylene has * character whilst the lowest energy ultra-violet spectral bands of the latter compounds stem from ^* transitions.

---

Zusammenfassung Valenzelektronenrechnungen nach Pople-Segal-Santry wurden für Äthylen und Vinylborane durchgeführt. Danach hat der niedrigste angeregte Zustand von Äthylen ^*-Charakter, während die längstwellige UV-Bande der Vinylborane einem ^* -Übergang entspricht.

---

Résumé Calculs de l'énergie pour les états fondamentaux et excités et de l'éthylène et des vinylboranes substitués. Utilisation de la méthode de Pople-Ségal-Santry. L'état excité le plus bas pour l'éthylène résulte d'une transition ^* , alors qu'il résulte d'une transition ^* pour les vinylboranes.

     

Donor properties of the nitrone function in copper(II) complexes of some 2-hydroxy-1-naphthylnitrones

Summary Copper(II) complexes of the type CuL₂, 2H₂O and CuL₂. Py where L=-(2-hydroxy-1-naphthyl)-N-R-nitrone (R= methyl, phenyl and variously substituted phenyls) have been isolated and characterised. They have normal magnetic moments. Their ligand field spectra indicate an octahedral geometry for the dihydrates and a five-coordinate environment for the pyridine adducts. Increased (C=N) and considerably decreased (N-O) frequencies in these complexes reveal the presence of - and -interactions of the ligand with copper through nitrone oxygen. The effect of pyridine adduct formation is to increase the Cu-O -interaction.     

Ionization potentials of halides. Substituent effects in Cl-, Br-, and I-centered radical cations

The first vertical ionization potentials (I) of halides HalX (Hal = Cl, Br, I; X is an inorganic or organic substituent) are linearly related to the inductive (_I), resonance (_R ⁺), and polarizability () constants of the substituents X (I = a + b_I + c_R ⁺ + d). As the atomic number of the Hal element in the Hal^·+X radical cations increases, the inductive interaction is strengthened while the polarizability interaction is weakened. Conjugation remains virtually independent of the Hal atom. The resonance _R ⁺-constants of the MX₃ (M = Si, Ge, Sn, Pb) substituents bound to the Hal^·+ radical cation centers were first calculated.     

State of components in group IV A metal modified nickel catalysts prepared via decomposition of metal complexes

The dispersity and state of components in (M+Ni)/SiO₂ catalysts (M=Ge, Sn, Pb), prepared via the reduction of anchored complexes, have been studied by chemisorption and electron microscopy. High dispersity of metallic particles (6Å) has been revealed. According to Mössbauer spectroscopy, in (Ni+Sn)/SiO₂ catalysts reduced at 873 K, a partial reduction of Sn to the metallic state is observed.

---

(M+Ni)/SiO₂ ( M=Ge, Sn, Pb), , , - . 873 ° K (Sn+Ni)/SiO₂ , , , 6 Å.

     

The use of thermal analysis in medical science with special reference to nephroliths

The applications of thermal methods in medical science have been summarized, with special regard to kidney stones. Complex thermal analysis can be used successfully for examination of human and animal urinary calculi, bones, odontoliths biological tissues (proteins, skin, callus, nail) etc.

---

Zusammenfassung Es wurden die Anwendungen der Thermoanalyse auf medizinischem Gebiet unter besonderer Berücksichtigung von Nierensteinen zusammenfassend behandelt. Komplexe thermoanalytische Methoden eignen sich zur Prüfung von menschlichen und tierischen Harnsteinen, Knochen, Zahnstein, biologischem Gewebe (Proteine, Haut, Nägel, usw.)

---

Résumé Revue des applications des méthodes thermoanalytiques dans le domaine médical avec mention particulière pour les calculs rénaux. L'emploi des méthodes d'analyse thermique mixtes donnent de bons résultats pour l'examen des calculs rénaux animaux et humains, du tartre dentaire et des tissus biologiques (protéines, peau, ongles), etc.

---

, . , (, , , ) .

     

High temperature thermal decomposition of propane

The thermal decomposition of propane has been studied by pulse chromatographic method within the temperature range of 975–1083 K. The kinetic parameters of the reaction have been determined.

---

- 975–1083 . .

     

Spectroscopic studies of the state of Cu2+ ions in Cu?Zn?Al oxide catalysts

ESR and electronic spectroscopy have reveled that in low-temperature ZnO the copper ions form Cu–O–Cu type cluster structures with highly covalent bonds and strong exchange interaction between the ions. The nearer environment of the Cu²⁺ ions is an octahedron with distortion towards square planar coordination.

---

, ZnO Cu–O–Cu . Cu²⁺- , .

     

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.     

Photoelectron spectra of vinyl tellurides

The lowest energy band in the photoelectron (PE) spectra of alkyl vinyl tellurides is attributed to-MO with predominant contribution from the p_z-AO of the tellurium atom. The second and fourth lowest energy bands correspond to-MO. An additional-MO is located between these-MO. The introduction of a second vinyl group hardly affects the HOMO. The heterocyclization of divinyl telluride has a large perturbation effect. Nevertheless, divinyl telluride and tellurophene have the same type of orbital structure.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 935–939, April, 1991.     

New models of monooxygenase on the basis of Sn(II) compounds

The data on the selectivity of various C–H bonds and the stereochemical course of the reaction in the known chemical systems simulating monooxygenase, do not agree with the oxenoid mechanism postulated for these reactions, but correspond to the interaction of saturated hydrocarbons with the OH radical intermediate. On the basis of organic compounds of Sn(II) in aprotic media, new systems have been developed which selectively oxidize alkanes to alcohols in the presence of O₂ in the coupled process and display many characteristics of the oxenoid reactions.

---

C–H , , , , . (II) , .

     

Spectroscopic study of compounds possessing a bond of an element of group IVB with hydrogen

Conclusions The frequencies of the valence vibrations of the Si-H bond in trisubstituted silanes depends not only on the inductive effect of substituents, but also on the effects of d-p interaction, ,- and p,-conjugation. An analysis was made of the relative contributions of these effects, depending on the nature of the substituent.For the preceding communications, see [1, 2].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 544–550, March, 1971.     

Theoretical electronic transition probabilities of heteronuclear diatomic molecules

Dipole strengths of various heteronuclear diatomic molecules are calculated for high and low energy transitions of one spectral type, 1-1, -. Through the use of increasingly accurate ground state wavefunctions it is possible to display the sensitivity of the transition probabilities to known approximations in the wavefunction. Selfconsistent field and configuration interaction effects are compared and contrasted.

---

Zusammenfassung Dipolstärken von zweiatomigen Molekülen mit verschiedenen Kernen wurden für Übergänge vom Typ 1-1, - mit großer und kleiner Energiedifferenz berechnet. In die Funktionen für den Grundzustand war eine unterschiedlich große Anzahl von Konfigurationen einbezogen worden, so daß die Abhängigkeit der Übergangswahrscheinlichkeiten vom Approximationsgrad verfolgt werden konnte. In der Diskussion wurden SCF- und CI-Effekte unterschieden.

---

Résumé Les forces d'oscilateurs dipolaires de diverses molécules diatomiques hétéronucléaires sont calculées pour les transitions de basse et haute énergie d'un type spectral 1-1, -. Par utilisation de fonctions d'onde de l'état fondamental de plus en plus précises il est possible de montrer la sensibilité des probabilités de transition aux approximations connues sur la fonction d'onde. Les effets liés au champ S.C.F. et à l'interaction de configuration sont comparés et différenciés.

---

---

Work Supported by the National Science Foundation.     

Ligand oxidation as a method for intramolecular activation of metal complexes

The results of investigations of organometallic and coordination compounds whose ligands contain redox fragments based on 2,6-di-tert-butylphenol and linked to the metal by various coordinating groups are summarized. The redox properties of -aryl, - and -allyl complexes, -diketonates, hydrazides, hydroxamates, glyoximates, and metalloporphyrins and metallophthalocyanines are considered. The possibility of changing the reactivity of organometallic and coordination compounds by changing the magnetic state due to oxidation of the redox-active phenolic group in the ligand is demonstrated. It is proposed to use ligand oxidation as a method for intramolecular activation of metal complexes.