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dc.contributor.author
Mola, Joaquim
dc.contributor.author
Pujol, David
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Rodríguez, Montserrat
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Romero, Isabel
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Sala, Xavier
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Katz, Néstor Eduardo
dc.contributor.author
Parella, Teodor
dc.contributor.author
Benet Buchholz, Jordi
dc.contributor.author
Fontrodona, Xavier
dc.contributor.author
Llobet, Antoni
dc.date.available
2018-08-08T20:17:25Z
dc.date.issued
2009-09
dc.identifier.citation
Mola, Joaquim; Pujol, David; Rodríguez, Montserrat; Romero, Isabel; Sala, Xavier; et al.; Synthesis and structure of novel RuII-N≡C-Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effects; Csiro Publishing; Australian Journal of Chemistry; 62; 12; 9-2009; 1675-1683
dc.identifier.issn
0004-9425
dc.identifier.uri
http://hdl.handle.net/11336/54674
dc.description.abstract
The synthesis and isolation of new RuIIacetonitrile complexes, of general formula trans,fac-[Ru(bpea)(B)(MeCN)](BF4)2 (bpea = N,N-bis(2-pyridylmethyl)ethylamine; B = bpy, 2,2′-bipyridine, 4; B = dppe, 1,2-bis(diphenylphosphino)ethane, 5), together with a synthetic intermediate trans,fac-[Ru(NO3)(bpea)(dppe)](BF4), 6, are described. Ru(bpea)Cl3, 1, is used as the starting material for the synthesis of all complexes 2-6 presented in this paper, which are characterized by analytical, spectroscopic (IR, UV/Vis, 1D and 2D NMR), and electrochemical techniques (cyclic voltammetry). Furthermore, complexes 4, 5, and 6 have also been characterized in the solid state by single crystal X-ray diffraction analysis. Their structures show a distorted octahedral geometry where the bpea ligand binds in a facial mode, the bidentate ligands bpy and dppe bind in a chelate manner, and finally the MeCN or the NO3 - ligand occupy the sixth position of the octahedral Ru metal centre. The kinetics of the basic hydrolysis of the coordinated MeCN ligand for complexes 4 and 5 and for the related complex [Ru(phen)(MeCN)([9]aneS3)](BF4) 2, 7, which contains the 1,4,7-trithiacyclonane ligand ([9]aneS 3) and 1,10-phenanthroline (phen) is also described. Second-order rate constants for acetonitrile hydrolysis measured at 25°C of k = 1.01 10-3 M-1 s-1 for 4, 1.08 10-4 M -1 s-1 for 5, and 6.8 10-3 M-1 s-1 for 7, have been obtained through UV-vis spectroscopy. Activation parameters have also been determined over the temperature range 25.0-45.0°C and agree with a mechanism that involves an associative rate-determining step. Finally the electronic and steric influence of the auxiliary ligands on this reaction for the above and related complexes is discussed.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Csiro Publishing
dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Ruthenium
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Hydrolysis
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Spectroscopy
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Otras Ciencias Químicas
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Ciencias Químicas
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CIENCIAS NATURALES Y EXACTAS
dc.title
Synthesis and structure of novel RuII-N≡C-Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effects
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2018-08-06T14:10:38Z
dc.journal.volume
62
dc.journal.number
12
dc.journal.pagination
1675-1683
dc.journal.pais
Australia
dc.journal.ciudad
Collingwood
dc.description.fil
Fil: Mola, Joaquim. Universidad de Girona; España
dc.description.fil
Fil: Pujol, David. Universidad de Girona; España
dc.description.fil
Fil: Rodríguez, Montserrat. Universidad de Girona; España
dc.description.fil
Fil: Romero, Isabel. Universidad de Girona; España
dc.description.fil
Fil: Sala, Xavier. Institut Català d'Investigació Química; España
dc.description.fil
Fil: Katz, Néstor Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; Argentina
dc.description.fil
Fil: Parella, Teodor. Universitat Autònoma de Barcelona; España
dc.description.fil
Fil: Benet Buchholz, Jordi. Institut Català d'Investigació Química; España
dc.description.fil
Fil: Fontrodona, Xavier. Universidad de Girona; España
dc.description.fil
Fil: Llobet, Antoni. Institut Català d'Investigació Química; España
dc.journal.title
Australian Journal of Chemistry
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/http://www.publish.csiro.au/CH/CH08563
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/https://doi.org/10.1071/CH08563
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