Intervalence electron transfer through a thiolate bridge ligand
| dc.contributor.author | Díaz, C | |
| dc.contributor.author | Arancibia, A | |
| dc.date.accessioned | 2025-01-21T01:31:04Z | |
| dc.date.available | 2025-01-21T01:31:04Z | |
| dc.date.issued | 2000 | |
| dc.description.abstract | The reaction of Cp(dppe)FeI with the ligands 2,2'- and 4,4'-dithiobispyridine (S-2(Py)(2)) give the mononuclear or binuclear complexes of the type [Cp(dppe)Fe-S-2(Py)(2)]PF6, [Cp(dppe)Fe-SPy]PF6 or [{Cp(dppe)Fe}(2)-mu -SPy](PF6)(2) depending on the reaction condition. Reaction of Cp(dppe)FeI with dithiobispyridines in presence of TIPF6 as halide abstractor and using CH2Cl2 as a solvent gives the complexes [Cp(dppe)Fe-4.4'-S-2(Py)(2))(2)]PF6 (1) and [CpFe(dppe)-2,2'-S-2(Py)(2)]PF6 (2) whereas the same reaction using CH3OH as a solvent and NH4PF6 as the halide abstractor leads to the formation of the Fe-III-thiolate complex [Cp(dppe)Fe-2,2'-SPy]PF6 (3) and the mixed-valence complex [Cp(dppe)Fe-III-mu SPy-Fe-II(dppe)Cp](PF6)(2) (4). Magnetic and ESR measurements are in agreement with one unpaired electron delocalized between them. Mossbauer data indicate clearly the presence of two different iron sites, each one of the N-bonded and S-bonded iron atoms, with intermediate oxidation state Fe-II-Fe-III. An electron transfer intervalence absorption was observed for this complex at 780 nm (in CH2Cl2). By applying the Hush theory the intervalence parameters were obtained; alpha = 0.028, H-ab = 361 cm(-1) which indicate Class II Robin-Day. Estimation of the rate electron transfer affords a value k(th) = 6.5 x 10(6) s(-1). Solvent effect on the intervalence transition follow the Hush prediction for high dielectric constants solvents which permit the evaluation of the outer and inner-sphere reorganizational parameters, which were analyzed and discussed. The electronic interaction parameters compare well with those found for electron transfer in metalloproteins. (C) 2000 Elsevier Science B.V. All rights reserved. | |
| dc.fuente.origen | WOS | |
| dc.identifier.issn | 0277-5387 | |
| dc.identifier.uri | https://repositorio.uc.cl/handle/11534/96973 | |
| dc.identifier.wosid | WOS:000166750400006 | |
| dc.issue.numero | 28 | |
| dc.language.iso | en | |
| dc.pagina.final | 2687 | |
| dc.pagina.inicio | 2679 | |
| dc.revista | Polyhedron | |
| dc.rights | acceso restringido | |
| dc.subject | thiolate-bridged complexes | |
| dc.subject | mixed-valence | |
| dc.subject | electron-transfer | |
| dc.subject | iron | |
| dc.subject.ods | 12 Responsible Consumption and Production | |
| dc.subject.odspa | 12 Producción y consumo responsable | |
| dc.title | Intervalence electron transfer through a thiolate bridge ligand | |
| dc.type | artículo | |
| dc.volumen | 19 | |
| sipa.index | WOS | |
| sipa.trazabilidad | WOS;2025-01-12 |