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Investigations on the structure of complex compounds by radioisotope exchange. The structure of cyanonitrosyl complexes; Recherches sur la structure des complexes par echange de radioisotopes - Structure des complexes cyanonitrosyliques; Issledovanie struktury slozhnykh soedinenij pri pomoshchi radioizotopnogo obmena - struktura slozhnykh tsianonitrozilovykh soedinenij; Estudio de la estructura de complejos por intercambio radioisotopico - Estructura de los complejos cianonitrosilicos

Conference:

Abstract

The nitrosyl group as the complex ligand is of particular interest because of its structure as well as its ability to form NO{sup -} or NO{sup +} groups. To study the electronic structure of K{sub 3}Mn(CN){sub 6} and K{sub 3}Mn(CN){sub 5}NO, the valency of the metal and the bonding type, investigations have been carried out by applying the method of radioisotopic exchange, as well as other physico-chemical methods. It has been found that by introducing the nitrosyl group into the hexacyanate ion, the stability of the complex is largely enhanced both in the solid state and in solution. This observation was confirmed by investigation of exchange kinetics in the systems: (I) K{sub 3}Mn(CN){sub 6} + KC{sup 14}N and (II) K{sub 3}Mn(CN){sub 5}NO + KC{sup 14}N In both cases, the exchange reactions are of first order, taken as a function of time, but differ considerably in their velocities, as well as in their activation energies. The anion Mn(CN){sub 5}NO{sup -3} is sensitive to light, so that the exchange reaction is photochemical in character. The ratio of the exchange velocity constants in the dark and at standardized illumination is 1:100. The first exchange reaction (I) proceeds according to the association mechanism while  More>>
Authors:
Jezowska-Trzeblatowska, B; Ziolkowski, J [1] 
  1. University of Wroclaw (Poland)
Publication Date:
Mar 15, 1962
Product Type:
Conference
Resource Relation:
Conference: Conference on the Use of Radioisotopes in the Physical Sciences and Industry, Copenhagen (Denmark), 6-17 Sep 1960; Other Information: 5 figs, 10 tabs, 16 refs; Related Information: In: Radioisotopes in the Physical Sciences and Industry. Proceedings of the Conference on the Use of Radioisotopes in the Physical Sciences and Industry. V. III| 652 p.
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 07 ISOTOPES AND RADIATION SOURCES; ACTIVATION ENERGY; ANIONS; COMPLEXES; CYANIDES; DISSOCIATION; ELECTRONIC STRUCTURE; KINETICS; LIGANDS; PARTITION; PHOTOCHEMISTRY; RADIOISOTOPES; SHELLS; SOLIDS; STABILITY; TIME DEPENDENCE
OSTI ID:
22025730
Research Organizations:
International Atomic Energy Agency, Vienna (Austria); United Nations Educational, Scientific and Cultural Organization, Paris (France)
Country of Origin:
IAEA
Language:
English
Other Identifying Numbers:
Other: ISSN 0074-1884; TRN: XA12N1746113023
Submitting Site:
INIS
Size:
page(s) 269-281
Announcement Date:
Jan 16, 2013

Conference:

Citation Formats

Jezowska-Trzeblatowska, B, and Ziolkowski, J. Investigations on the structure of complex compounds by radioisotope exchange. The structure of cyanonitrosyl complexes; Recherches sur la structure des complexes par echange de radioisotopes - Structure des complexes cyanonitrosyliques; Issledovanie struktury slozhnykh soedinenij pri pomoshchi radioizotopnogo obmena - struktura slozhnykh tsianonitrozilovykh soedinenij; Estudio de la estructura de complejos por intercambio radioisotopico - Estructura de los complejos cianonitrosilicos. IAEA: N. p., 1962. Web.
Jezowska-Trzeblatowska, B, & Ziolkowski, J. Investigations on the structure of complex compounds by radioisotope exchange. The structure of cyanonitrosyl complexes; Recherches sur la structure des complexes par echange de radioisotopes - Structure des complexes cyanonitrosyliques; Issledovanie struktury slozhnykh soedinenij pri pomoshchi radioizotopnogo obmena - struktura slozhnykh tsianonitrozilovykh soedinenij; Estudio de la estructura de complejos por intercambio radioisotopico - Estructura de los complejos cianonitrosilicos. IAEA.
Jezowska-Trzeblatowska, B, and Ziolkowski, J. 1962. "Investigations on the structure of complex compounds by radioisotope exchange. The structure of cyanonitrosyl complexes; Recherches sur la structure des complexes par echange de radioisotopes - Structure des complexes cyanonitrosyliques; Issledovanie struktury slozhnykh soedinenij pri pomoshchi radioizotopnogo obmena - struktura slozhnykh tsianonitrozilovykh soedinenij; Estudio de la estructura de complejos por intercambio radioisotopico - Estructura de los complejos cianonitrosilicos." IAEA.
@misc{etde_22025730,
title = {Investigations on the structure of complex compounds by radioisotope exchange. The structure of cyanonitrosyl complexes; Recherches sur la structure des complexes par echange de radioisotopes - Structure des complexes cyanonitrosyliques; Issledovanie struktury slozhnykh soedinenij pri pomoshchi radioizotopnogo obmena - struktura slozhnykh tsianonitrozilovykh soedinenij; Estudio de la estructura de complejos por intercambio radioisotopico - Estructura de los complejos cianonitrosilicos}
author = {Jezowska-Trzeblatowska, B, and Ziolkowski, J}
abstractNote = {The nitrosyl group as the complex ligand is of particular interest because of its structure as well as its ability to form NO{sup -} or NO{sup +} groups. To study the electronic structure of K{sub 3}Mn(CN){sub 6} and K{sub 3}Mn(CN){sub 5}NO, the valency of the metal and the bonding type, investigations have been carried out by applying the method of radioisotopic exchange, as well as other physico-chemical methods. It has been found that by introducing the nitrosyl group into the hexacyanate ion, the stability of the complex is largely enhanced both in the solid state and in solution. This observation was confirmed by investigation of exchange kinetics in the systems: (I) K{sub 3}Mn(CN){sub 6} + KC{sup 14}N and (II) K{sub 3}Mn(CN){sub 5}NO + KC{sup 14}N In both cases, the exchange reactions are of first order, taken as a function of time, but differ considerably in their velocities, as well as in their activation energies. The anion Mn(CN){sub 5}NO{sup -3} is sensitive to light, so that the exchange reaction is photochemical in character. The ratio of the exchange velocity constants in the dark and at standardized illumination is 1:100. The first exchange reaction (I) proceeds according to the association mechanism while the second one (II) possesses a composite association- dissociation mechanism. Analysis of the partition of activity within the cyanide groups undergoing exchange in the isotopic equilibrium state, revealed the identity of at least four cyanide groups. The high stability of the nitrosyl complex, as compared with the hexacyanate, was proved in various ways. All this pointed to a NO{sup -} structure in the complex. Previous research has shown that the nitrosyl group is coordinated as NO{sup +}. This suggests a resonance structure of the complex by assuming the resonance of an electronic pair between the T{sub 2g} shell of the central atom and the p shell of the nitrogen atom. (author) [French] Le groupe nitrosyle en tant que coordinat du complexe cyanonitrosylique est particulierement interessant en raison de sa structure et de son aptitude a former des groupes NO{sup -} ou NO{sup +}. Pour etudier la structure electronique du K{sub 3}Mn(CN){sub 6} et du K{sub 3}Mn(CN){sub 5}NO, la valence du metaf et le type de liaison, des recherches ont ete faites au moyen de la methode de l'echange de radioisotopes, ainsi que par d'autres methodes physicochimiques. On a constate qu'en introduisant le groupe nitrosyle dans l'ion d'hexacyanate, la stabilite du complexe est sensiblement renforcee, a l'etat solide comme a l'etat de solution. Cette observation s'est trouvee confirmee par des recherches sur la cinetique des echanges intervenant dans les systemes suivants: (I) K{sub 3}Mn(CN){sub 6} + KC{sup 14}N (II) K{sub 3}Mn(CN){sub 5}NO + KC{sup 14}N. Dans les deux cas, les reactions d'echange sont du premier ordre, mais leurs vitesses et leurs energies d'activation sout extremement differentes. L'anion Mn(CN){sub 5}NO{sub 3} etant sensible a la lumiere, la reaction d'echange est de caractere photochimique. Le rapportdes constantes de vitesse d'echange dans l'obscurite et sous eclairage normalise est de 1:100. La premiere reaction d'echange (I) se produit conformement au mecanisme d'association, tandis que la seconde (II) suit un mecanisme combine association/ dissociation. L'analyse de la distribution de l'activite, dans les groupes cyanure qui subissent un echange a l'etat d'equilibre isotopique, a revele l'existence d'au moins quatre groupes cyanure distincts. La grande stabilite du complexe nitrosylique, en comparaison de celle de l'hexacyanate, a ete prouvee par differentes methodes. Tout cela semble indiquer une structure NO{sup -} dans le complexe. Des recherches anterieures ont montre que le groupe nitrosyle est coordonne sous forme de NO{sup +}. Cela donne a penser que le complexe possede une structure de resonance, si l'on admet la resonance d'une paire d'electrons entre la couche T{sub 2g} de l'atome central et la couche p de l'atome d'azote. (author) [Spanish] El grupo nitrosilo puede actuar en las dos formas NO{sup -} y NO{sup +} y esta propiedad, junto con su estructura, le confiere particular importancia como grupo ligante. Los autores han estudiado la estructura electronica del K{sub 3}Mn(CN){sub 6} y del K{sub 3}Mn(CN){sub 5}NO, la valencia del metal y el tipo de enlace, empleando metodos de intercambio radioisotopico y otras tecnicas fisicoquimicas. Encuentran que la introduccion del grupo nitrosilo en el ion hexacianuro aumenta notablemente la estabilidad del complejo, tanto en estado solido como en solucion. Esta observacion queda corroborada por el estudio de la cinetica de intercambio de los sistemas: (I) K{sub 3}Mn(CN){sub 6} + K{sup 14}CN (II) K{sub 3}Mn(CN){sub 5}NO + K{sup 14}CN En ambos casos, las reacciones de intercambio son de primer orden, pero sus velocidades y sus energias de activacion respectivas son muy distintas. El anion [Mn(CN){sub 5} NO]{sub 3} - es fotosensible, de modo que la reaccion de intercambio tiene caracter fotoquimieo. La razon entre las constantes de velocidad del intercambio en la oscuridad y baj o una iluminacion tipo es 1:100. La primera reaccion de intercambio (I) transcurre segun un mecanismo de asociacion, mientras que la segunda (II) obedece a un mecanismo compuesto de asociacion-disociacion. En el estado de equilibrio isotopico, el analisis de la distribucion de la actividad entre los grupos cianuro que sufren el intercambio revela la identidad de por lo menos cuatro de los grupos cianuro. Por diferentes metodos se pudo demostrar que el complejo nitrosilado posee una estabilidad mucho mayor que el hexacianuro. Todo lo precedente indica la presencia de una estructura NO{sup -} en el complejo. Las investigaciones anteriores habian revelado que el grupo nitrosilo esta coordinado como NO{sup +}. Ello sugiere la existencia de ima estructura resonante para el complejo, admitiendo la resonancia de un par electronico entre la capa T{sub 2g} del atomo central y la capa p del atomo de nitrogeno. (author) [Russian] V kachestve slozhnogo svyazuyushchego zvena nitrozilovaya gruppa predstavlyaet osobyj interes kak po svoej strukture, tak i blagodarya svoemu svojstvu obrazovyvat' gruppy NO{sup -} i NO{sup +}. Dlya issledovaniya ehlektronnoj struktury K{sub 3}Mn(CN){sub 6} i K{sub 3}Mn(CN){sub 6}NO, valentnosti metalla i kharaktera soedinenij byli proizvedeny issledovaniya pri pomoshchi metoda radioizotopnogo obmena, a takzhe i drugikh fiziko-khimicheskikh metodov. Bylo obnaruzheno, chto dobavlenie nitrozilovoj gruppy k ionam geksatsionata znachitel'no uvelichivaet ustojchivost' soedineniya kak v tverdom sostoyanii, tak i v rastvore. EHto nablyudenie bylo podtverzhdeno issledovaniem kinetiki obmena v sistemakh: (I) K{sub 3}Mn(CN){sub 6} + KC{sup 14}N; (II) K{sub 3}Mn(CN){sub 5}NO + KC{sup 14}N. V oboikh sluchayakh reaktsii obmena v funktsii vremeni yavlyayutsya reaktsiyami pervogo poryadka, no oni znachitel'no otlichayutsya drug ot druga po skorosti. EHnergii aktivatsii ehtikh reaktsij ravny E{sub 1}=8,5 kilokalorij na molekulu i E{sub 11}=22,8 kilokalorij na molekulu. Anion Mn(CN){sub 5}NO{sub 3} svetochuvstvitelen, tak chto reaktsiya obmena nosit fotokhimicheskij kharakter. Sootnoshenie postoyannykh skorostej obmena v temnote i pri standartizirovannom osveshchenii ravno 1:100. Pervaya reaktsiya obmena (I) proiskhodit po tipu assotsiatsii, togda kak vtoraya reaktsiya (II) sleduet slozhnomu mekhanizmu assotsiatsii i dissotsiatsii. Analiz raspredeleniya aktivnosti mezhdu tsianistymi gruppami, podvergayushchimisya obmenu v sostoyanii izotopnogo ravnovesiya, obnaruzhil identichnost' po men'shej mere chetyrekh tsianistykh grupp. Bol'shaya ustojchivost' nitrozilovykh soedinenij po sravneniyu s geksatsianatami, a takzhe otsutstvie vtorichnykh dissotsiatsij byli podtverzhdeny razlichnymi metodami. Vse ehto ukazyvaet na strukturu NO{sup -} kompleksa. Predydushchie issledovaniya pokazali, chto nitrozilovaya gruppa koordiniruetsya v vide NO{sup +}. EHto ukazyvaet na rezonansnuyu strukturu slozhnogo soedineniya, iskhodya iz gipotezy nalichiya rezonansa ehlektronnoj pary mezhdu T{sub 2g}-obolochkoj tsentral'nogo atoma i p-obraznoj obolochkoj atoma azota. (author)}
place = {IAEA}
year = {1962}
month = {Mar}
}