Dinuclear Pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture

A series of dinuclear pyridine-4-thiolate rhodium and iridium compounds [M(μ-4-Spy)(diolef)]2 (diolef = 1,5-cyclooctadiene, cod; M = Rh (1), Ir (2); 2,5-norbornadiene, nbd; M = Rh (3)) have been prepared by reaction of Li(4-Spy) with the appropriate compound [M(μ-Cl)(diolef)]2 (M = Rh, Ir). The dinu...

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Autores: Ferrer García, Montserrat, Gómez Bautista, Daniel, Gutiérrez i Currius, Albert, Miranda, José R., Orduña Marco, Guillermo, Oro, Luis A., Pérez Torrente, Jesús J., Rossell Alfonso, Oriol, García Orduña, Pilar, Lahoz, Fernando J.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2014
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/128138
Acceso en línea:https://hdl.handle.net/2445/128138
Access Level:acceso abierto
Palabra clave:Lligands
Complexos metàl·lics
Rodi
Iridi
Química supramolecular
Ligands
Metal complexes
Rhodium
Iridium
Supramolecular chemistry
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spelling Dinuclear Pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architectureFerrer García, MontserratGómez Bautista, DanielGutiérrez i Currius, AlbertMiranda, José R.Orduña Marco, GuillermoOro, Luis A.Pérez Torrente, Jesús J.Rossell Alfonso, OriolGarcía Orduña, PilarLahoz, Fernando J.LligandsComplexos metàl·licsRodiIridiQuímica supramolecularLigandsMetal complexesRhodiumIridiumSupramolecular chemistryA series of dinuclear pyridine-4-thiolate rhodium and iridium compounds [M(μ-4-Spy)(diolef)]2 (diolef = 1,5-cyclooctadiene, cod; M = Rh (1), Ir (2); 2,5-norbornadiene, nbd; M = Rh (3)) have been prepared by reaction of Li(4-Spy) with the appropriate compound [M(μ-Cl)(diolef)]2 (M = Rh, Ir). The dinuclear compound [Rh(μ-4-Spy)(CO)(PPh3)]2 (4) has been obtained by reaction of [Rh(acac)(CO)(PPh3] with 4-pySH. Compounds 1-4 have been assessed as metalloligands in self-assembly reactions with the cis-blocked [M(cod)(NCCH3)2](BF4) (M = Rh (a) and M = Ir (b)) and [M(H2O)2(dppp)](OTf)2 (M = Pd (c), Pt (d)) (dppp = 1,3-bis(diphenylphosphino)propane) acceptors. Homo [{M2(μ-4-Spy)2(cod)2}2{M(cod)}2](BF4)2 (M = Rh (1a)2, and M = Ir (2b)2), and hetero [{Rh2(μ-4-Spy)2(cod)2}2{Ir(cod)}2](BF4)2 (1b)2, [{Rh2(μ-4-Spy)2(cod)2}2{M'(dppp)}2](OTf)4 ( M' = Pd (1c)2 and M'= Pt (1d)2) and [{Ir2(μ-4-Spy)2(cod)2}2{M'(dppp)}2](OTf)4 ( M' = Pd (2c)2 and M'= Pt (2d)2) hexanuclear metallomacrocycles have been obtained. NMR spectroscopy, in combination with ESI mass spectrometry has been used to elucidate the nature of the metalloligands and their respective supramolecular assemblies. Most of synthesized species have shown to be non-rigid in solution and their fluxional behavior has been studied by VT 1H NMR spectroscopy. An X-ray diffraction study on the assemblies (1a)2 and (1d)2 revealed the formation of rectangular (9.6 x 6.6 Å) hexanuclear metallomacrocycles with alternating dinuclear (Rh2) and mononuclear (Rh or Pt) corners. The hexanuclear core is supported by four pyridine-4-thiolate linkers, which are bonded through the thiolate moiety to the dinuclear rhodium units, exhibiting a bent-anti arrangement, and through the peripheral pyridinic nitrogen atoms to the mononuclear corners.American Chemical Society2019201920142019info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion13 p.application/pdfhttps://hdl.handle.net/2445/128138Articles publicats en revistes (Química Inorgànica i Orgànica)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésVersió postprint del document publicat a: https://doi.org/10.1021/ic402838yInorganic Chemistry, 2014, vol. 53, num. 3, p. 1699-1711https://doi.org/10.1021/ic402838y(c) American Chemical Society , 2014info:eu-repo/semantics/openAccessoai:recercat.cat:2445/1281382026-05-29T05:05:01Z
dc.title.none.fl_str_mv Dinuclear Pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture
title Dinuclear Pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture
spellingShingle Dinuclear Pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture
Ferrer García, Montserrat
Lligands
Complexos metàl·lics
Rodi
Iridi
Química supramolecular
Ligands
Metal complexes
Rhodium
Iridium
Supramolecular chemistry
title_short Dinuclear Pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture
title_full Dinuclear Pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture
title_fullStr Dinuclear Pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture
title_full_unstemmed Dinuclear Pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture
title_sort Dinuclear Pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture
dc.creator.none.fl_str_mv Ferrer García, Montserrat
Gómez Bautista, Daniel
Gutiérrez i Currius, Albert
Miranda, José R.
Orduña Marco, Guillermo
Oro, Luis A.
Pérez Torrente, Jesús J.
Rossell Alfonso, Oriol
García Orduña, Pilar
Lahoz, Fernando J.
author Ferrer García, Montserrat
author_facet Ferrer García, Montserrat
Gómez Bautista, Daniel
Gutiérrez i Currius, Albert
Miranda, José R.
Orduña Marco, Guillermo
Oro, Luis A.
Pérez Torrente, Jesús J.
Rossell Alfonso, Oriol
García Orduña, Pilar
Lahoz, Fernando J.
author_role author
author2 Gómez Bautista, Daniel
Gutiérrez i Currius, Albert
Miranda, José R.
Orduña Marco, Guillermo
Oro, Luis A.
Pérez Torrente, Jesús J.
Rossell Alfonso, Oriol
García Orduña, Pilar
Lahoz, Fernando J.
author2_role author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Lligands
Complexos metàl·lics
Rodi
Iridi
Química supramolecular
Ligands
Metal complexes
Rhodium
Iridium
Supramolecular chemistry
topic Lligands
Complexos metàl·lics
Rodi
Iridi
Química supramolecular
Ligands
Metal complexes
Rhodium
Iridium
Supramolecular chemistry
description A series of dinuclear pyridine-4-thiolate rhodium and iridium compounds [M(μ-4-Spy)(diolef)]2 (diolef = 1,5-cyclooctadiene, cod; M = Rh (1), Ir (2); 2,5-norbornadiene, nbd; M = Rh (3)) have been prepared by reaction of Li(4-Spy) with the appropriate compound [M(μ-Cl)(diolef)]2 (M = Rh, Ir). The dinuclear compound [Rh(μ-4-Spy)(CO)(PPh3)]2 (4) has been obtained by reaction of [Rh(acac)(CO)(PPh3] with 4-pySH. Compounds 1-4 have been assessed as metalloligands in self-assembly reactions with the cis-blocked [M(cod)(NCCH3)2](BF4) (M = Rh (a) and M = Ir (b)) and [M(H2O)2(dppp)](OTf)2 (M = Pd (c), Pt (d)) (dppp = 1,3-bis(diphenylphosphino)propane) acceptors. Homo [{M2(μ-4-Spy)2(cod)2}2{M(cod)}2](BF4)2 (M = Rh (1a)2, and M = Ir (2b)2), and hetero [{Rh2(μ-4-Spy)2(cod)2}2{Ir(cod)}2](BF4)2 (1b)2, [{Rh2(μ-4-Spy)2(cod)2}2{M'(dppp)}2](OTf)4 ( M' = Pd (1c)2 and M'= Pt (1d)2) and [{Ir2(μ-4-Spy)2(cod)2}2{M'(dppp)}2](OTf)4 ( M' = Pd (2c)2 and M'= Pt (2d)2) hexanuclear metallomacrocycles have been obtained. NMR spectroscopy, in combination with ESI mass spectrometry has been used to elucidate the nature of the metalloligands and their respective supramolecular assemblies. Most of synthesized species have shown to be non-rigid in solution and their fluxional behavior has been studied by VT 1H NMR spectroscopy. An X-ray diffraction study on the assemblies (1a)2 and (1d)2 revealed the formation of rectangular (9.6 x 6.6 Å) hexanuclear metallomacrocycles with alternating dinuclear (Rh2) and mononuclear (Rh or Pt) corners. The hexanuclear core is supported by four pyridine-4-thiolate linkers, which are bonded through the thiolate moiety to the dinuclear rhodium units, exhibiting a bent-anti arrangement, and through the peripheral pyridinic nitrogen atoms to the mononuclear corners.
publishDate 2014
dc.date.none.fl_str_mv 2014
2019
2019
2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/128138
url https://hdl.handle.net/2445/128138
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: https://doi.org/10.1021/ic402838y
Inorganic Chemistry, 2014, vol. 53, num. 3, p. 1699-1711
https://doi.org/10.1021/ic402838y
dc.rights.none.fl_str_mv (c) American Chemical Society , 2014
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) American Chemical Society , 2014
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 13 p.
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv Articles publicats en revistes (Química Inorgànica i Orgànica)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.81155

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