Three redox states of metallonitrosyls in aqueous solution

This contribution deals with the structure and reactivity of bound nitrosyl in transition-metal centers (group 8: Fe, Ru, Os). The focus is set on pseudooctahedral nitrosyl-complexes with coordination number 5 and 6, containing ancillary coligands of both heme- and nonheme type. The discussion is or...

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Autores principales: Bari, S.E., Olabe, J.A., Slep, L.D.
Formato: SER
Materias:
Nitrosyl
Nitrosyl hydride
Nitroxyl
NO-complexes
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_08988838_v67_n_p87_Bari
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling todo:paper_08988838_v67_n_p87_Bari2023-10-03T15:44:04Z Three redox states of metallonitrosyls in aqueous solution Bari, S.E. Olabe, J.A. Slep, L.D. Nitrosyl Nitrosyl hydride Nitroxyl NO-complexes This contribution deals with the structure and reactivity of bound nitrosyl in transition-metal centers (group 8: Fe, Ru, Os). The focus is set on pseudooctahedral nitrosyl-complexes with coordination number 5 and 6, containing ancillary coligands of both heme- and nonheme type. The discussion is organized in terms of Enemark and Feltham's classification, selecting complexes within the {MNO}n framework (n=6, 7, and 8). The examples have been chosen for a best description of the electronic structures in terms of modern structural, spectroscopical, and computational methodologies. The selected {MNO}6,7,8 species reflect the occurrence of three redox states of bound nitrosyl, frequently (though not always) described as NO+, NO, and NO- for n=6, 7, and 8, respectively. The analysis is centered on the members of a series of complexes for which the three redox states have been observed on the same platform, viz., [Fe(CN)5(NO)]2,3,4- and [Ru(Me3[9]aneN3)(bpy)(NO)]3,2,1+, in aqueous solutions. The influence of the donor-acceptor character of the coligands is specifically addressed with emphasis on the ligand trans- to nitrosyl, showing that the latter group may exert a delabilizing influence (as NO+), as well as a labilizing one (NO-≫NO) on the trans-ligand. On the other hand, typical electrophilic reactivity patterns (toward different nucleophiles) are analyzed for M-NO+, and nucleophilic reactivity (with O2) is described for the reduced species, M-NO and M-(NO-). In the latter case, protonation is described by characterizing the bound HNO species. Important differences are highlighted in the chemistry of bound NO- and HNO, revealing the strong and mild reductant abilities of these species, respectively. The chemistry is analyzed in terms of the biological relevance to the behavior of nitrite- and NO-reductases and other NO-related enzymes. © 2015 Elsevier Inc. Fil:Bari, S.E. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Olabe, J.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Slep, L.D. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. SER info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_08988838_v67_n_p87_Bari
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Nitrosyl
Nitrosyl hydride
Nitroxyl
NO-complexes
spellingShingle Nitrosyl
Nitrosyl hydride
Nitroxyl
NO-complexes
Bari, S.E.
Olabe, J.A.
Slep, L.D.
Three redox states of metallonitrosyls in aqueous solution
topic_facet Nitrosyl
Nitrosyl hydride
Nitroxyl
NO-complexes
description This contribution deals with the structure and reactivity of bound nitrosyl in transition-metal centers (group 8: Fe, Ru, Os). The focus is set on pseudooctahedral nitrosyl-complexes with coordination number 5 and 6, containing ancillary coligands of both heme- and nonheme type. The discussion is organized in terms of Enemark and Feltham's classification, selecting complexes within the {MNO}n framework (n=6, 7, and 8). The examples have been chosen for a best description of the electronic structures in terms of modern structural, spectroscopical, and computational methodologies. The selected {MNO}6,7,8 species reflect the occurrence of three redox states of bound nitrosyl, frequently (though not always) described as NO+, NO, and NO- for n=6, 7, and 8, respectively. The analysis is centered on the members of a series of complexes for which the three redox states have been observed on the same platform, viz., [Fe(CN)5(NO)]2,3,4- and [Ru(Me3[9]aneN3)(bpy)(NO)]3,2,1+, in aqueous solutions. The influence of the donor-acceptor character of the coligands is specifically addressed with emphasis on the ligand trans- to nitrosyl, showing that the latter group may exert a delabilizing influence (as NO+), as well as a labilizing one (NO-≫NO) on the trans-ligand. On the other hand, typical electrophilic reactivity patterns (toward different nucleophiles) are analyzed for M-NO+, and nucleophilic reactivity (with O2) is described for the reduced species, M-NO and M-(NO-). In the latter case, protonation is described by characterizing the bound HNO species. Important differences are highlighted in the chemistry of bound NO- and HNO, revealing the strong and mild reductant abilities of these species, respectively. The chemistry is analyzed in terms of the biological relevance to the behavior of nitrite- and NO-reductases and other NO-related enzymes. © 2015 Elsevier Inc.
format SER
author Bari, S.E.
Olabe, J.A.
Slep, L.D.
author_facet Bari, S.E.
Olabe, J.A.
Slep, L.D.
author_sort Bari, S.E.
title Three redox states of metallonitrosyls in aqueous solution
title_short Three redox states of metallonitrosyls in aqueous solution
title_full Three redox states of metallonitrosyls in aqueous solution
title_fullStr Three redox states of metallonitrosyls in aqueous solution
title_full_unstemmed Three redox states of metallonitrosyls in aqueous solution
title_sort three redox states of metallonitrosyls in aqueous solution
url http://hdl.handle.net/20.500.12110/paper_08988838_v67_n_p87_Bari
work_keys_str_mv AT barise threeredoxstatesofmetallonitrosylsinaqueoussolution
AT olabeja threeredoxstatesofmetallonitrosylsinaqueoussolution
AT slepld threeredoxstatesofmetallonitrosylsinaqueoussolution
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