Coordination of aza heterocycles with macroheterocyclic metal complexes in amphiprotic media: III. Kinetics and mechanism of inner-sphere ligand exchange in (tetraphenylporphyrinato)chromium(III)

Inner-sphere replacement of alcohols by imidazole and its derivatives in the complex (acetato)-(tetraphenylporphyrinato)chromium(III) was studied by electronic absorption spectroscopy. The rate constants and activation parameters of the process were calculated. The entering ligand structure was shown to affect the reaction rate, while the alcohol nature (departing ligand) does not influence the kinetic parameters of the process to an appreciable extent. Regression analysis revealed participation of imidazole and ethanol in the rate-determining stages. The kinetic equation for the inner-sphere axial substitution implies interaction of a free alcohol molecule with that coordinated to chromium, followed by replacement of the associate by the heteroring. Mathematical processing of the kinetic data in terms of the proposed solvolytic association-dissociation mechanism gave the rate constants for particular stages of the process and showed an extremal relation between the rate constant and composition of the solvent.     

Researches on synthetic dyes

Reaction of phenyl-ß-naphthylamines with formaldehyde and acetone in the presence of HCl and nitrobenzene in butanol solution leads to cyclization involving the naphthalene and phenyl rings, and formation of N-aryllepidine salts. 15 lepidine and 5, 6-benzoepidine salts are synthesized and characterized by their UV absorption spectra, as well as by their picrates.For Part LIII see [3].     

On the exceptional zeros of cross-products of derivatives of spherical Bessel functions

The lowest zeros of the cross-products of derivatives of spherical Bessel functions are not obtainable from a McMahon-type formula. This paper derives an analytical approximation for these lowest, exceptional, zeros, through to 4th order in a parameter specifying the thinness of the corresponding concentric spherical region.

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Zusammenfassung Die kleinsten Nullstellen der Kreuzprodukte der Ableitungen von spherischen Bessel-funktionen können nicht durch eine Formel von McMahon Typ erhalten werden. Durch eine Entwicklung bis zu vierter Ordnung in einem Parameter proportional zur Dicke des zugeordneten spherischen Gebietes berechnen wir eine analytische Näherung für diese kleinsten, außergewöhnlichen, Nullstellen.

     

The Factorization of Queueing Equations and Their Interpretation

There are many queueing systems, including the M ^x /M ^y /c queue, the GI ^x /M/c queue and the M/D/c queue, in which the distribution of the queue length at certain epochs is determined by a Markov chain with the following structure. Except for a number of boundary states, all columns of the transition matrix are identical except for a shift which assures that there is always the same element occupying the main diagonal. This paper describes how one can find the equilibrium distribution for such Markov chains. Typically, this problem is solved by factorizing of a certain expression characterizing the repeated columns. In this paper, we show that this factorization has a probabilistic significance and we use this result to develop new approaches for finding the equilibrium distribution in question.     

Reactions of Carboxymethyl Polysaccharides and Their Ethyl Esters with Amines

The reaction of carboxymethyl polysaccharides and their ethyl esters with amines was studied with the aim to determine how the structure of the polymeric acylating agent affects the composition of the reaction products.     

Pyrazolines — Derivatives of 2-nitrochalcone

By the reaction of 2-nitrochalcone with hydrazine hydrate, 5-(2-nitrophenyl)-3-phenyl-1H-2-pyrazoline (I) and the hydrazone of 3-(5-(2-nitrophenyl)-3-phenyl-2-pyrazolin-1-yl)-3-(2-nitrophenyl)propiophenol (II) have been prepared. The acylation of both compounds I and II leads to N-acyl derivatives of the first. The acylating ability of formamide and N,N-dimethylformamide was observed in reactions with pyrazoline I. An x-ray structural study was carried out on compound II.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 360–366, March, 1993.     

Mass spectrometric study of mixed fluorinated rare earth element β-diketonates with triphenylphosphine oxide

A series of new adducts of fluorinated REE -diketonates with triphenylphosphine oxide was synthesized. The paths of their fragmentation under electron impact were investigated. It was shown that in contrast to the complex with 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane-4,6-dione, the complexes of europium with 1-trifluoromethoxy-1,1-difluoro-5,5-dimethylhexane-2,4-dione and 1, 1,1-trifluoro-5,5-dimethylhexane-2,4-dione form dimeric associates in the gaseous phase. The reasons for this difference in the behavior of the complexes and the possible structure of one of the dimers are discussed.Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 26, No. 2, March–April, 1990.     

The discovery of nuclear fission 50 years ago a few remarks

A historical account on the details of the discovery of nuclear fission in 1939 is given.After an address presented at the INS Conference on Nuclear Science and Technology in India-Past, Present and Future BARC, Bombay, 18th January 1989.