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Article: Structural and mechanistic studies of co-ordination compounds. Part 24. Application of cyclic voltammetry to study the chelation effect on acid hydrolysis of some cis- and trans-ruthenium(II) amine complexes

TitleStructural and mechanistic studies of co-ordination compounds. Part 24. Application of cyclic voltammetry to study the chelation effect on acid hydrolysis of some cis- and trans-ruthenium(II) amine complexes
Authors
Issue Date1980
PublisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
Citation
Journal Of The Chemical Society, Dalton Transactions, 1980 n. 1, p. 128-133 How to Cite?
AbstractFormal reduction potentials Ef of a series of tertramine ruthenium(III) complexes of the type cis- and trans-[RuL (A)X]n+ have been determined by cyclic voltammetry (c.v.) in aqueous solution. In general, for a given pair of unidentate ligands A and X, the Ef values increase with increased chelation fo L: (NH3)4 < (en)2 (en = H2NCH2CH2NH2) < 2,3,2-tet(3,7-diazanonane-1,9-diamine, RS isomer) < cyclam (1,4,8,11-tetra-azacyclotetradecane). On the other hand, for a given tetramine L, the Ef values vary with the nature of A and X in the following manner: dihalogeno- < aquahalogeno- < diaqua-couples, and chloro- < bromo- < isothiocyanato-couples. The Ef values of cis isomers are greater than those of the trans counterparts. The kinetics of aquation of some ruthenium(II) complexes of the type trans-[RuLX2] (X = Cl or Br) have also been followed over a range of temperature by the c.v. technique.These reactions are stereoretentive with negative entropies of activation, the first-order rate constants, k1, decrease with increased chelation, and the complexes are less labile than the corresponding cis, isomers similar features to those of the corresponding cobalt(III) and ruthenium(III) complexes. A dissociative machanism with a square-pyramidal intermediate is assumed for these reactions. The importance of solvation, nephelauxetic, and σ-trans effects has been invoked to explain the above thermodynamic and kinetic behaviour of these ruthenium complexes.
Persistent Identifierhttp://hdl.handle.net/10722/168267
ISSN
2002 Impact Factor: 3.023
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorPoon, CKen_US
dc.contributor.authorChe, CMen_US
dc.contributor.authorKan, YPen_US
dc.date.accessioned2012-10-08T03:16:49Z-
dc.date.available2012-10-08T03:16:49Z-
dc.date.issued1980en_US
dc.identifier.citationJournal Of The Chemical Society, Dalton Transactions, 1980 n. 1, p. 128-133en_US
dc.identifier.issn1472-7773en_US
dc.identifier.urihttp://hdl.handle.net/10722/168267-
dc.description.abstractFormal reduction potentials Ef of a series of tertramine ruthenium(III) complexes of the type cis- and trans-[RuL (A)X]n+ have been determined by cyclic voltammetry (c.v.) in aqueous solution. In general, for a given pair of unidentate ligands A and X, the Ef values increase with increased chelation fo L: (NH3)4 < (en)2 (en = H2NCH2CH2NH2) < 2,3,2-tet(3,7-diazanonane-1,9-diamine, RS isomer) < cyclam (1,4,8,11-tetra-azacyclotetradecane). On the other hand, for a given tetramine L, the Ef values vary with the nature of A and X in the following manner: dihalogeno- < aquahalogeno- < diaqua-couples, and chloro- < bromo- < isothiocyanato-couples. The Ef values of cis isomers are greater than those of the trans counterparts. The kinetics of aquation of some ruthenium(II) complexes of the type trans-[RuLX2] (X = Cl or Br) have also been followed over a range of temperature by the c.v. technique.These reactions are stereoretentive with negative entropies of activation, the first-order rate constants, k1, decrease with increased chelation, and the complexes are less labile than the corresponding cis, isomers similar features to those of the corresponding cobalt(III) and ruthenium(III) complexes. A dissociative machanism with a square-pyramidal intermediate is assumed for these reactions. The importance of solvation, nephelauxetic, and σ-trans effects has been invoked to explain the above thermodynamic and kinetic behaviour of these ruthenium complexes.en_US
dc.languageengen_US
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/daltonen_US
dc.relation.ispartofJournal of the Chemical Society, Dalton Transactionsen_US
dc.titleStructural and mechanistic studies of co-ordination compounds. Part 24. Application of cyclic voltammetry to study the chelation effect on acid hydrolysis of some cis- and trans-ruthenium(II) amine complexesen_US
dc.typeArticleen_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1039/DT9800000128en_US
dc.identifier.scopuseid_2-s2.0-37049110945en_US
dc.identifier.issue1en_US
dc.identifier.spage128en_US
dc.identifier.epage133en_US
dc.identifier.isiWOS:A1980JB98100023-
dc.publisher.placeUnited Kingdomen_US
dc.identifier.scopusauthoridPoon, CK=7202673504en_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US
dc.identifier.scopusauthoridKan, YP=23070538900en_US

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