Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes
Autor(a) principal: | |
---|---|
Data de Publicação: | 2014 |
Outros Autores: | , , , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10400.21/4943 |
Resumo: | fac-[MBr(CO)(3)(pypzH)] (M = Mn, Re; pypzH = (3-(2-pyridyl) pyrazole) complexes are prepared from fac[ MBr(CO)(3)(NCMe)(2)] and pypzH. The result of their deprotonation depends on the metallic substrate: the rhenium complex affords cleanly the bimetallic compound [fac-{Re(CO)(3)(mu(2)-pypz)}] 2 (mu(2)-pypz = mu(2)-3-(2pyridyl-. 1N) pyrazolate-2. 1N), which was crystallographically characterized, whereas a similar manganese complex was not detected. When two equivalents of pyridylpyrazolate are used, polymetallic species [fac-M(CO) 3(mu(2)-pypz)(mu(3)-pypz) M'] (mu(3)-pypz = mu(3)-3-(2-pyridyl-kappa N-1) pyrazolate-1 kappa 2N, N: 2. 1N:; M = Mn, M' = Li, Na, K; M = Re, M' = Na) are obtained. The crystal structures of the manganese carbonylate complexes were determined. The lithium complex is a monomer containing one manganese and one lithium atom, whereas the sodium and potassium complexes are dimers and reveal an unprecedented coordination mode for the bridging 3-(2-pyridyl) pyrazolate ligand, where the nitrogen of the pyridyl fragment and the nitrogen-1 of pyrazolate are chelated to manganese atoms, and each nitrogen-2 of pyrazolate is coordinated to two alkaline atoms. The polymetallic carbonylate complexes are unstable in solution and evolve spontaneously to [fac-{Re(CO) 3(mu(2)-pypz)}](2) or to the trimetallic paramagnetic species [MnII(mu(2)-pypz) 2{fac-{MnI(CO) 3(mu(2)-pypz)}(2)}]. The related complex cis-[MnCl2(pypzH)(2)] was also synthesized and structurally characterized. The electrochemical behavior of the new homo-and heteropolymetallic 3-(2-pyridyl) pyrazolate complexes has been studied and details of their redox properties are reported. |
id |
RCAP_429081d4385f9799a0f357a598a7317c |
---|---|
oai_identifier_str |
oai:repositorio.ipl.pt:10400.21/4943 |
network_acronym_str |
RCAP |
network_name_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository_id_str |
7160 |
spelling |
Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexesTricarbonylrhenium(I) bromide complexesCoordination compoundsCrystal structureX-rayMolecular structureElectrochemical parametrizationSpectroscopic propertiesAsymmetric catalysisPyrazole complexesRu(II) complexesfac-[MBr(CO)(3)(pypzH)] (M = Mn, Re; pypzH = (3-(2-pyridyl) pyrazole) complexes are prepared from fac[ MBr(CO)(3)(NCMe)(2)] and pypzH. The result of their deprotonation depends on the metallic substrate: the rhenium complex affords cleanly the bimetallic compound [fac-{Re(CO)(3)(mu(2)-pypz)}] 2 (mu(2)-pypz = mu(2)-3-(2pyridyl-. 1N) pyrazolate-2. 1N), which was crystallographically characterized, whereas a similar manganese complex was not detected. When two equivalents of pyridylpyrazolate are used, polymetallic species [fac-M(CO) 3(mu(2)-pypz)(mu(3)-pypz) M'] (mu(3)-pypz = mu(3)-3-(2-pyridyl-kappa N-1) pyrazolate-1 kappa 2N, N: 2. 1N:; M = Mn, M' = Li, Na, K; M = Re, M' = Na) are obtained. The crystal structures of the manganese carbonylate complexes were determined. The lithium complex is a monomer containing one manganese and one lithium atom, whereas the sodium and potassium complexes are dimers and reveal an unprecedented coordination mode for the bridging 3-(2-pyridyl) pyrazolate ligand, where the nitrogen of the pyridyl fragment and the nitrogen-1 of pyrazolate are chelated to manganese atoms, and each nitrogen-2 of pyrazolate is coordinated to two alkaline atoms. The polymetallic carbonylate complexes are unstable in solution and evolve spontaneously to [fac-{Re(CO) 3(mu(2)-pypz)}](2) or to the trimetallic paramagnetic species [MnII(mu(2)-pypz) 2{fac-{MnI(CO) 3(mu(2)-pypz)}(2)}]. The related complex cis-[MnCl2(pypzH)(2)] was also synthesized and structurally characterized. The electrochemical behavior of the new homo-and heteropolymetallic 3-(2-pyridyl) pyrazolate complexes has been studied and details of their redox properties are reported.Royal Society of ChemistryRCIPLArroyo, MartaGomez-Iglesias, PatriciaAnton, NoeliaGarcia-Rodriguez, RaulAlegria, ElisabetePombeiro, ArmandoMiguel, DanielVillafane, Fernando2015-08-24T11:30:12Z20142014-01-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10400.21/4943engARROYO, Marta; [et al] – Homo-And Heteropolymetallic 3-(2-Pyridyl)Pyrazolate Manganese and Rhenium complexes. Dalton Transactions. ISSN: 1477-9226. Vol. 43, nr. 10 (2104), pp. 4009-40201477-922610.1039/c3dt53439ametadata only accessinfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2023-08-03T09:47:41Zoai:repositorio.ipl.pt:10400.21/4943Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T20:14:18.112551Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes |
title |
Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes |
spellingShingle |
Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes Arroyo, Marta Tricarbonylrhenium(I) bromide complexes Coordination compounds Crystal structure X-ray Molecular structure Electrochemical parametrization Spectroscopic properties Asymmetric catalysis Pyrazole complexes Ru(II) complexes |
title_short |
Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes |
title_full |
Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes |
title_fullStr |
Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes |
title_full_unstemmed |
Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes |
title_sort |
Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes |
author |
Arroyo, Marta |
author_facet |
Arroyo, Marta Gomez-Iglesias, Patricia Anton, Noelia Garcia-Rodriguez, Raul Alegria, Elisabete Pombeiro, Armando Miguel, Daniel Villafane, Fernando |
author_role |
author |
author2 |
Gomez-Iglesias, Patricia Anton, Noelia Garcia-Rodriguez, Raul Alegria, Elisabete Pombeiro, Armando Miguel, Daniel Villafane, Fernando |
author2_role |
author author author author author author author |
dc.contributor.none.fl_str_mv |
RCIPL |
dc.contributor.author.fl_str_mv |
Arroyo, Marta Gomez-Iglesias, Patricia Anton, Noelia Garcia-Rodriguez, Raul Alegria, Elisabete Pombeiro, Armando Miguel, Daniel Villafane, Fernando |
dc.subject.por.fl_str_mv |
Tricarbonylrhenium(I) bromide complexes Coordination compounds Crystal structure X-ray Molecular structure Electrochemical parametrization Spectroscopic properties Asymmetric catalysis Pyrazole complexes Ru(II) complexes |
topic |
Tricarbonylrhenium(I) bromide complexes Coordination compounds Crystal structure X-ray Molecular structure Electrochemical parametrization Spectroscopic properties Asymmetric catalysis Pyrazole complexes Ru(II) complexes |
description |
fac-[MBr(CO)(3)(pypzH)] (M = Mn, Re; pypzH = (3-(2-pyridyl) pyrazole) complexes are prepared from fac[ MBr(CO)(3)(NCMe)(2)] and pypzH. The result of their deprotonation depends on the metallic substrate: the rhenium complex affords cleanly the bimetallic compound [fac-{Re(CO)(3)(mu(2)-pypz)}] 2 (mu(2)-pypz = mu(2)-3-(2pyridyl-. 1N) pyrazolate-2. 1N), which was crystallographically characterized, whereas a similar manganese complex was not detected. When two equivalents of pyridylpyrazolate are used, polymetallic species [fac-M(CO) 3(mu(2)-pypz)(mu(3)-pypz) M'] (mu(3)-pypz = mu(3)-3-(2-pyridyl-kappa N-1) pyrazolate-1 kappa 2N, N: 2. 1N:; M = Mn, M' = Li, Na, K; M = Re, M' = Na) are obtained. The crystal structures of the manganese carbonylate complexes were determined. The lithium complex is a monomer containing one manganese and one lithium atom, whereas the sodium and potassium complexes are dimers and reveal an unprecedented coordination mode for the bridging 3-(2-pyridyl) pyrazolate ligand, where the nitrogen of the pyridyl fragment and the nitrogen-1 of pyrazolate are chelated to manganese atoms, and each nitrogen-2 of pyrazolate is coordinated to two alkaline atoms. The polymetallic carbonylate complexes are unstable in solution and evolve spontaneously to [fac-{Re(CO) 3(mu(2)-pypz)}](2) or to the trimetallic paramagnetic species [MnII(mu(2)-pypz) 2{fac-{MnI(CO) 3(mu(2)-pypz)}(2)}]. The related complex cis-[MnCl2(pypzH)(2)] was also synthesized and structurally characterized. The electrochemical behavior of the new homo-and heteropolymetallic 3-(2-pyridyl) pyrazolate complexes has been studied and details of their redox properties are reported. |
publishDate |
2014 |
dc.date.none.fl_str_mv |
2014 2014-01-01T00:00:00Z 2015-08-24T11:30:12Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10400.21/4943 |
url |
http://hdl.handle.net/10400.21/4943 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
ARROYO, Marta; [et al] – Homo-And Heteropolymetallic 3-(2-Pyridyl)Pyrazolate Manganese and Rhenium complexes. Dalton Transactions. ISSN: 1477-9226. Vol. 43, nr. 10 (2104), pp. 4009-4020 1477-9226 10.1039/c3dt53439a |
dc.rights.driver.fl_str_mv |
metadata only access info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
metadata only access |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Royal Society of Chemistry |
publisher.none.fl_str_mv |
Royal Society of Chemistry |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
instname_str |
Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
repository.mail.fl_str_mv |
|
_version_ |
1799133400554012672 |