Three redox states of metallonitrosyls in aqueous solution

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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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Autor principal: Bari, S.E
Otros Autores: Olabe, J.A, Slep, L.D
Formato: Capítulo de libro
Lenguaje:Inglés
Publicado: Academic Press Inc. 2015
Acceso en línea:Registro en Scopus
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100 1 |a Bari, S.E. 
245 1 0 |a Three redox states of metallonitrosyls in aqueous solution 
260 |b Academic Press Inc.  |c 2015 
270 1 0 |m Olabe, J.A.; Departamento de Química Inorgánica, Analítica y Química Física and INQUIMAE, Universidad de Buenos Aires/CONICET, Facultad de Ciencias Exactas y Naturales, Pabellón 2, Ciudad Universitaria, Argentina; email: olabe@qi.fcen.uba.ar 
506 |2 openaire  |e Política editorial 
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520 3 |a 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.  |l eng 
593 |a Departamento de Química Inorgánica, Analítica y Química Física and INQUIMAE, Universidad de Buenos Aires/CONICET, Facultad de Ciencias Exactas y Naturales, Pabellón 2, Ciudad Universitaria, Autonomous City of Buenos Aires, C1428EHA, Argentina 
690 1 0 |a NITROSYL 
690 1 0 |a NITROSYL HYDRIDE 
690 1 0 |a NITROXYL 
690 1 0 |a NO-COMPLEXES 
700 1 |a Olabe, J.A. 
700 1 |a Slep, L.D. 
773 0 |d Academic Press Inc., 2015  |g v. 67  |h pp. 87-144  |p Adv. Inorg. Chem.  |x 08988838  |t Advances in Inorganic Chemistry 
856 4 1 |u https://www.scopus.com/inward/record.uri?eid=2-s2.0-84921520823&doi=10.1016%2fbs.adioch.2014.10.001&partnerID=40&md5=e9b502a8d8a3ae13498d3745a6fbac94  |y Registro en Scopus 
856 4 0 |u https://doi.org/10.1016/bs.adioch.2014.10.001  |y DOI 
856 4 0 |u https://hdl.handle.net/20.500.12110/paper_08988838_v67_n_p87_Bari  |y Handle 
856 4 0 |u https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08988838_v67_n_p87_Bari  |y Registro en la Biblioteca Digital 
961 |a paper_08988838_v67_n_p87_Bari  |b paper  |c PE 
962 |a info:eu-repo/semantics/article  |a info:ar-repo/semantics/artículo  |b info:eu-repo/semantics/publishedVersion 
999 |c 74603 

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