On the Synthesis and Chemical Behaviour of the Elusive Bis(hydrosulfido)-Bridged Dinuclear Rhodium(I) Complexes [{Rh(μ-SH)(CO)(PR3)}2]

11 páginas, 6 figuras, 5 tablas, 4 esquemas.

Detalles Bibliográficos
Autores: Pérez-Torrente, Jesús J., Jiménez, M. Victoria, Hernandez-Gruel, Marc A. F., Fabra-Caro, María J., Lahoz, Fernando J., Oro, Luis A.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2009
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/57973
Acceso en línea:http://hdl.handle.net/10261/57973
Access Level:acceso abierto
Palabra clave:Bridging ligands
Clusters compounds
Rhodium
Sulfur
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spelling On the Synthesis and Chemical Behaviour of the Elusive Bis(hydrosulfido)-Bridged Dinuclear Rhodium(I) Complexes [{Rh(μ-SH)(CO)(PR3)}2]Pérez-Torrente, Jesús J.Jiménez, M. VictoriaHernandez-Gruel, Marc A. F.Fabra-Caro, María J.Lahoz, Fernando J.Oro, Luis A.Bridging ligandsClusters compoundsRhodiumSulfur11 páginas, 6 figuras, 5 tablas, 4 esquemas.Several bis(hydrosulfido)-bridged dinuclear rhodium(I) compounds, [{Rh(μ-SH)(L)2}2], have been prepared from rhodium(I) acetylacetonato complexes, [Rh(acac)(L)2], and H2S(g). Reaction of [Rh(acac){P(OPh)3}2] with H2S(g) affords the dinuclear bis(hydrosulfido)-bridged compound [{Rh(μ-SH){P(OPh)3}2}2] (1). However, reaction of complexes [Rh(acac)(CO)(PR3)] with H2S(g) gives the dinuclear compound [{Rh(μ-SH)(CO)(PR3)}2] (R=Cy, 2; R=Ph, 4) and the trinuclear cluster [Rh3(μ-H)(μ3-S)2(CO)3(PR3)3] (R=Cy, 3; R=Ph, 5). The selective synthesis of both type of compounds has been carried out by control of the H2S(g) concentration in the reaction media. The trinuclear hydrido–sulfido cluster [Rh3(μ-H)(μ3-S)2(CO)3(PPh3)3] (5) has been also obtained by reaction of [{Rh(μ-SH)(CO)(PPh3)}2] (4) with [Rh(acac)(CO)(PPh3)], proceeding through the trinuclear hydrosulfido–sulfido intermediate [Rh3(μ3-SH)(μ3-S)(CO)3(PPh3)3]. The molecular structures of complexes 1 and 3 have been determined by X-ray diffraction methods. Compound 1 is stable in solution, but complexes 2 and 4 slowly transform in solution into the trinuclear hydrido–sulfido clusters 3 and 5, respectively, with the release of H2S(g) in a reversible way. 1H NMR kinetic experiments for the transformation of 4 into 5 have revealed that this transformation follows second-order-type kinetic. The following activation parameters, ΔH≠=24±3 kJ mol−1 and of ΔS≠=−223±8 J K−1 mol−1, have been calculated from the determination of the second-order rate constants in the temperature range 30–45 °C. The large negative value of the activation entropy is consistent with an associative character of the rate-determining step. A plausible multistep mechanism based on the chemical behaviour of hydrosulfido–metal complexes and compatible with the kinetic behaviour has been proposed.The financial support from Ministerio de Educación y Ciencia (MEC/ FEDER) is gratefully acknowledged (Project CTQ2006-03973/BQU).Peer reviewedWiley-VCHMinisterio de Educación y Ciencia (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]201220122009info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/57973reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Ingléshttp://dx.doi.org/10.1002/chem.200902249Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/579732026-05-22T06:33:51Z
dc.title.none.fl_str_mv On the Synthesis and Chemical Behaviour of the Elusive Bis(hydrosulfido)-Bridged Dinuclear Rhodium(I) Complexes [{Rh(μ-SH)(CO)(PR3)}2]
title On the Synthesis and Chemical Behaviour of the Elusive Bis(hydrosulfido)-Bridged Dinuclear Rhodium(I) Complexes [{Rh(μ-SH)(CO)(PR3)}2]
spellingShingle On the Synthesis and Chemical Behaviour of the Elusive Bis(hydrosulfido)-Bridged Dinuclear Rhodium(I) Complexes [{Rh(μ-SH)(CO)(PR3)}2]
Pérez-Torrente, Jesús J.
Bridging ligands
Clusters compounds
Rhodium
Sulfur
title_short On the Synthesis and Chemical Behaviour of the Elusive Bis(hydrosulfido)-Bridged Dinuclear Rhodium(I) Complexes [{Rh(μ-SH)(CO)(PR3)}2]
title_full On the Synthesis and Chemical Behaviour of the Elusive Bis(hydrosulfido)-Bridged Dinuclear Rhodium(I) Complexes [{Rh(μ-SH)(CO)(PR3)}2]
title_fullStr On the Synthesis and Chemical Behaviour of the Elusive Bis(hydrosulfido)-Bridged Dinuclear Rhodium(I) Complexes [{Rh(μ-SH)(CO)(PR3)}2]
title_full_unstemmed On the Synthesis and Chemical Behaviour of the Elusive Bis(hydrosulfido)-Bridged Dinuclear Rhodium(I) Complexes [{Rh(μ-SH)(CO)(PR3)}2]
title_sort On the Synthesis and Chemical Behaviour of the Elusive Bis(hydrosulfido)-Bridged Dinuclear Rhodium(I) Complexes [{Rh(μ-SH)(CO)(PR3)}2]
dc.creator.none.fl_str_mv Pérez-Torrente, Jesús J.
Jiménez, M. Victoria
Hernandez-Gruel, Marc A. F.
Fabra-Caro, María J.
Lahoz, Fernando J.
Oro, Luis A.
author Pérez-Torrente, Jesús J.
author_facet Pérez-Torrente, Jesús J.
Jiménez, M. Victoria
Hernandez-Gruel, Marc A. F.
Fabra-Caro, María J.
Lahoz, Fernando J.
Oro, Luis A.
author_role author
author2 Jiménez, M. Victoria
Hernandez-Gruel, Marc A. F.
Fabra-Caro, María J.
Lahoz, Fernando J.
Oro, Luis A.
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Educación y Ciencia (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Bridging ligands
Clusters compounds
Rhodium
Sulfur
topic Bridging ligands
Clusters compounds
Rhodium
Sulfur
description 11 páginas, 6 figuras, 5 tablas, 4 esquemas.
publishDate 2009
dc.date.none.fl_str_mv 2009
2012
2012
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/57973
url http://hdl.handle.net/10261/57973
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv http://dx.doi.org/10.1002/chem.200902249
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Wiley-VCH
publisher.none.fl_str_mv Wiley-VCH
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,81155

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