Kinetics of formation, dissociation, and isomerization reactions in complexes of cyanopyridines and benzonitrile with pentacyanoruthenate(II)

The complexes of pentacyanoruthenate(II) with 3- and 4-cyanopyridines and benzonitrile have been prepared in aqueous solution by mixing [Ru(CN)<inf>5</inf>(H<inf>2</inf>O)]3- with the appropriate ligand. With the cyanopyridines, the reaction proceeds in two stages: the first...

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Autor principal: Olabe Iparraguirre, Jose Antonio
Publicado: 1989
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14727773_v_n10_p1973_Almaraz
http://hdl.handle.net/20.500.12110/paper_14727773_v_n10_p1973_Almaraz
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling paper:paper_14727773_v_n10_p1973_Almaraz2023-06-08T16:17:23Z Kinetics of formation, dissociation, and isomerization reactions in complexes of cyanopyridines and benzonitrile with pentacyanoruthenate(II) Olabe Iparraguirre, Jose Antonio The complexes of pentacyanoruthenate(II) with 3- and 4-cyanopyridines and benzonitrile have been prepared in aqueous solution by mixing [Ru(CN)<inf>5</inf>(H<inf>2</inf>O)]3- with the appropriate ligand. With the cyanopyridines, the reaction proceeds in two stages: the first corresponds to the formation of a mixture of pyridine- and nitrile-bonded isomers, and the second to the linkage isomerization of the unstable (nitrile-bonded) isomer to the stable one (pyridine-bonded). The complexes exhibit metal-to- ligand and intra-ligand charge-transfer absorptions. The rate constants for the formation, k<inf>f</inf>, and dissociation, k<inf>d</inf>, of all the complexes have been determined (25 °C), as well as the isomerization rate constant, k<inf>iso</inf>, for the cyanopyridine complexes. Activation parameters were obtained for the formation reaction of the mixture of isomers, as well as for the dissociation reactions of the stable, pyridine-bonded complexes. The results for the formation and dissociation reactions are analysed in terms of dissociative mechanisms. From k<inf>f</inf> and k<inf>d</inf>, values of K<inf>st</inf>, the stability constants of the different complexes, have been calculated. The discussion is supported by previous data obtained for related pentacyanoferrate(II) and penta-ammineruthenium(II) complexes. Thus, the influence of the metal centre, M, as well as that of the auxiliary ligands, X, on the spectral and substitution reactivity properties of MX<inf>5</inf>L systems is described. Fil:Olabe, J.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 1989 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14727773_v_n10_p1973_Almaraz http://hdl.handle.net/20.500.12110/paper_14727773_v_n10_p1973_Almaraz
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description The complexes of pentacyanoruthenate(II) with 3- and 4-cyanopyridines and benzonitrile have been prepared in aqueous solution by mixing [Ru(CN)<inf>5</inf>(H<inf>2</inf>O)]3- with the appropriate ligand. With the cyanopyridines, the reaction proceeds in two stages: the first corresponds to the formation of a mixture of pyridine- and nitrile-bonded isomers, and the second to the linkage isomerization of the unstable (nitrile-bonded) isomer to the stable one (pyridine-bonded). The complexes exhibit metal-to- ligand and intra-ligand charge-transfer absorptions. The rate constants for the formation, k<inf>f</inf>, and dissociation, k<inf>d</inf>, of all the complexes have been determined (25 °C), as well as the isomerization rate constant, k<inf>iso</inf>, for the cyanopyridine complexes. Activation parameters were obtained for the formation reaction of the mixture of isomers, as well as for the dissociation reactions of the stable, pyridine-bonded complexes. The results for the formation and dissociation reactions are analysed in terms of dissociative mechanisms. From k<inf>f</inf> and k<inf>d</inf>, values of K<inf>st</inf>, the stability constants of the different complexes, have been calculated. The discussion is supported by previous data obtained for related pentacyanoferrate(II) and penta-ammineruthenium(II) complexes. Thus, the influence of the metal centre, M, as well as that of the auxiliary ligands, X, on the spectral and substitution reactivity properties of MX<inf>5</inf>L systems is described.
author Olabe Iparraguirre, Jose Antonio
spellingShingle Olabe Iparraguirre, Jose Antonio
Kinetics of formation, dissociation, and isomerization reactions in complexes of cyanopyridines and benzonitrile with pentacyanoruthenate(II)
author_facet Olabe Iparraguirre, Jose Antonio
author_sort Olabe Iparraguirre, Jose Antonio
title Kinetics of formation, dissociation, and isomerization reactions in complexes of cyanopyridines and benzonitrile with pentacyanoruthenate(II)
title_short Kinetics of formation, dissociation, and isomerization reactions in complexes of cyanopyridines and benzonitrile with pentacyanoruthenate(II)
title_full Kinetics of formation, dissociation, and isomerization reactions in complexes of cyanopyridines and benzonitrile with pentacyanoruthenate(II)
title_fullStr Kinetics of formation, dissociation, and isomerization reactions in complexes of cyanopyridines and benzonitrile with pentacyanoruthenate(II)
title_full_unstemmed Kinetics of formation, dissociation, and isomerization reactions in complexes of cyanopyridines and benzonitrile with pentacyanoruthenate(II)
title_sort kinetics of formation, dissociation, and isomerization reactions in complexes of cyanopyridines and benzonitrile with pentacyanoruthenate(ii)
publishDate 1989
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14727773_v_n10_p1973_Almaraz
http://hdl.handle.net/20.500.12110/paper_14727773_v_n10_p1973_Almaraz
work_keys_str_mv AT olabeiparraguirrejoseantonio kineticsofformationdissociationandisomerizationreactionsincomplexesofcyanopyridinesandbenzonitrilewithpentacyanoruthenateii
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