Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O.

Detalhes bibliográficos
Autor(a) principal: Pepe, Iuri Muniz
Data de Publicação: 2011
Outros Autores: Doro, Fabio Gorzoni, Galembeck, Sergio Emanuel, Carlos, Rose M., Rocha, Zenis N. da, Bertotti, Mauro, Tfouni, Elia
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Institucional da UFBA
Texto Completo: http://repositorio.ufba.br/ri/handle/ri/14762
Resumo: p. 6420–6432
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spelling Pepe, Iuri MunizDoro, Fabio GorzoniGalembeck, Sergio EmanuelCarlos, Rose M.Rocha, Zenis N. daBertotti, MauroTfouni, Elia2014-03-20T12:29:38Z2014-03-20T12:29:38Z20111477-9226http://repositorio.ufba.br/ri/handle/ri/14762v. 40, n. 24p. 6420–6432Chemical reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam, fac-[Ru(NO)Cl2(κ3N4,N8,N11(1carboxypropyl)cyclam)]Cl·H2O((1-carboxypropyl)cyclam = 3-(1,4,8,11-tetraazacyclotetradecan-1-yl)propionic acid)), (I) are described. Chloride ligands do not undergo aquation reactions (at 25 °C, pH 3). The rate of nitric oxide (NO) dissociation (kobs-NO) upon reduction of I is 2.8 s−1 at 25 ± 1 °C (in 0.5 mol L−1HCl), which is close to the highest value found for related complexes. The uncoordinated carboxyl of I has a pKa of [similar]3.3, which is close to that of the carboxyl of the non coordinated (1-carboxypropyl)cyclam (pKa = 3.4). Two additional pKa values were found for I at [similar]8.0 and [similar]11.5. Upon electrochemical reduction or under irradiation with light (λirr = 350 or 520 nm; pH 7.4), I releases NO in aqueous solution. The cyclam ring N bound to the carboxypropyl group is not coordinated, resulting in a fac configuration that affects the properties and chemical reactivities of I, especially as NO donor, compared with analogous trans complexes. Among the computational models tested, the B3LYP/ECP28MDF, cc-pVDZ resulted in smaller errors for the geometry of I. The computational data helped clarify the experimental acid-base equilibria and indicated the most favourable site for the second deprotonation, which follows that of the carboxyl group. Furthermore, it showed that by changing the pH it is possible to modulate the electron density of I with deprotonation. The calculated NO bond length and the Ru/NO charge ratio indicated that the predominant canonical structure is [RuIIINO], but the Ru–NO bond angles and bond index (b.i.) values were less clear; the angles suggested that [RuIINO+] could contribute to the electronic structure of I and b.i. values indicated a contribution from [RuIVNO−]. Considering that some experimental data are consistent with a [RuIINO+] description, while others are in agreement with [RuIIINO], the best description for I would be a linear combination of the three canonical forms, with a higher weight for [RuIINO+] and [RuIIINO].Submitted by Edileide Reis (leyde-landy@hotmail.com) on 2014-03-20T12:29:38Z No. of bitstreams: 1 Iuri M. Pepe.pdf: 1077129 bytes, checksum: 6b79bb00725324853a601b90e317ac8b (MD5)Made available in DSpace on 2014-03-20T12:29:38Z (GMT). No. of bitstreams: 1 Iuri M. Pepe.pdf: 1077129 bytes, checksum: 6b79bb00725324853a601b90e317ac8b (MD5) Previous issue date: 2011http://dx.doi.org/ 10.1039/C0DT01541Ereponame:Repositório Institucional da UFBAinstname:Universidade Federal da Bahia (UFBA)instacron:UFBAReactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O.Dalton Transactionsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleBrasilinfo:eu-repo/semantics/openAccessengORIGINALIuri M. Pepe.pdfIuri M. Pepe.pdfapplication/pdf1077129https://repositorio.ufba.br/bitstream/ri/14762/1/Iuri%20M.%20Pepe.pdf6b79bb00725324853a601b90e317ac8bMD51LICENSElicense.txtlicense.txttext/plain1345https://repositorio.ufba.br/bitstream/ri/14762/2/license.txt0d4b811ef71182510d2015daa7c8a900MD52TEXTIuri M. Pepe.pdf.txtIuri M. 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dc.title.pt_BR.fl_str_mv Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O.
dc.title.alternative.pt_BR.fl_str_mv Dalton Transactions
title Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O.
spellingShingle Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O.
Pepe, Iuri Muniz
title_short Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O.
title_full Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O.
title_fullStr Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O.
title_full_unstemmed Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O.
title_sort Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O.
author Pepe, Iuri Muniz
author_facet Pepe, Iuri Muniz
Doro, Fabio Gorzoni
Galembeck, Sergio Emanuel
Carlos, Rose M.
Rocha, Zenis N. da
Bertotti, Mauro
Tfouni, Elia
author_role author
author2 Doro, Fabio Gorzoni
Galembeck, Sergio Emanuel
Carlos, Rose M.
Rocha, Zenis N. da
Bertotti, Mauro
Tfouni, Elia
author2_role author
author
author
author
author
author
dc.contributor.author.fl_str_mv Pepe, Iuri Muniz
Doro, Fabio Gorzoni
Galembeck, Sergio Emanuel
Carlos, Rose M.
Rocha, Zenis N. da
Bertotti, Mauro
Tfouni, Elia
description p. 6420–6432
publishDate 2011
dc.date.issued.fl_str_mv 2011
dc.date.accessioned.fl_str_mv 2014-03-20T12:29:38Z
dc.date.available.fl_str_mv 2014-03-20T12:29:38Z
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://repositorio.ufba.br/ri/handle/ri/14762
dc.identifier.issn.none.fl_str_mv 1477-9226
dc.identifier.number.pt_BR.fl_str_mv v. 40, n. 24
identifier_str_mv 1477-9226
v. 40, n. 24
url http://repositorio.ufba.br/ri/handle/ri/14762
dc.language.iso.fl_str_mv eng
language eng
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
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dc.publisher.country.fl_str_mv Brasil
dc.source.pt_BR.fl_str_mv http://dx.doi.org/ 10.1039/C0DT01541E
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