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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paper:paper_08988838_v67_n_p87_Bari2023-06-08T15:49:29Z Three redox states of metallonitrosyls in aqueous solution Bari, Sara Elizabeth Olabe Iparraguirre, Jose Antonio Slep, Leonardo Daniel 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. 2015 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08988838_v67_n_p87_Bari 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, Sara Elizabeth Olabe Iparraguirre, Jose Antonio Slep, Leonardo Daniel 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. |
author |
Bari, Sara Elizabeth Olabe Iparraguirre, Jose Antonio Slep, Leonardo Daniel |
author_facet |
Bari, Sara Elizabeth Olabe Iparraguirre, Jose Antonio Slep, Leonardo Daniel |
author_sort |
Bari, Sara Elizabeth |
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 |
publishDate |
2015 |
url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08988838_v67_n_p87_Bari http://hdl.handle.net/20.500.12110/paper_08988838_v67_n_p87_Bari |
work_keys_str_mv |
AT barisaraelizabeth threeredoxstatesofmetallonitrosylsinaqueoussolution AT olabeiparraguirrejoseantonio threeredoxstatesofmetallonitrosylsinaqueoussolution AT slepleonardodaniel threeredoxstatesofmetallonitrosylsinaqueoussolution |
_version_ |
1768546074959544320 |