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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
Title | 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 |
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Authors | |
Issue Date | 1980 |
Publisher | Royal 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? |
Abstract | Formal 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 Identifier | http://hdl.handle.net/10722/168267 |
ISSN | |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Poon, CK | en_US |
dc.contributor.author | Che, CM | en_US |
dc.contributor.author | Kan, YP | en_US |
dc.date.accessioned | 2012-10-08T03:16:49Z | - |
dc.date.available | 2012-10-08T03:16:49Z | - |
dc.date.issued | 1980 | en_US |
dc.identifier.citation | Journal Of The Chemical Society, Dalton Transactions, 1980 n. 1, p. 128-133 | en_US |
dc.identifier.issn | 1472-7773 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/168267 | - |
dc.description.abstract | Formal 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.language | eng | en_US |
dc.publisher | Royal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton | en_US |
dc.relation.ispartof | Journal of the Chemical Society, Dalton Transactions | en_US |
dc.title | 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 | en_US |
dc.type | Article | en_US |
dc.identifier.email | Che, CM:cmche@hku.hk | en_US |
dc.identifier.authority | Che, CM=rp00670 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1039/DT9800000128 | en_US |
dc.identifier.scopus | eid_2-s2.0-37049110945 | en_US |
dc.identifier.issue | 1 | en_US |
dc.identifier.spage | 128 | en_US |
dc.identifier.epage | 133 | en_US |
dc.identifier.isi | WOS:A1980JB98100023 | - |
dc.publisher.place | United Kingdom | en_US |
dc.identifier.scopusauthorid | Poon, CK=7202673504 | en_US |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_US |
dc.identifier.scopusauthorid | Kan, YP=23070538900 | en_US |
dc.identifier.issnl | 1364-5447 | - |