Widely differing stabilities of molecule-bridged cyanodiiron(III, II) species in non-aqueous solvents

The redox systems [(NC)5Fe(μ-L)Fe(CN)5])6-/5-/4- with L=pyrazine (1n), 4,4′-bipyridine (2n) or 1,2-bis(4-pyridyl)ethene (3n), and [(NC)4Fe(μ-bmtz)Fe(CN)4]5-/4-/3- (4n) with bmtz=3,6-bis(2-pyrimidyl)-1,2,4,5-tetrazine were studied in acetonitrile and other aprotic solvents. The comproportionation con...

Descripción completa

Guardado en:
Detalles Bibliográficos
Publicado: 1999
Materias:
Cyano complexes
Iron complexes
Mixed-valence complexes
Spectroelectrochemistry
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201693_v291_n1-2_p66_Ketterle
http://hdl.handle.net/20.500.12110/paper_00201693_v291_n1-2_p66_Ketterle
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_00201693_v291_n1-2_p66_Ketterle
record_format dspace
spelling paper:paper_00201693_v291_n1-2_p66_Ketterle2023-06-08T14:40:49Z Widely differing stabilities of molecule-bridged cyanodiiron(III, II) species in non-aqueous solvents Cyano complexes Iron complexes Mixed-valence complexes Spectroelectrochemistry The redox systems [(NC)5Fe(μ-L)Fe(CN)5])6-/5-/4- with L=pyrazine (1n), 4,4′-bipyridine (2n) or 1,2-bis(4-pyridyl)ethene (3n), and [(NC)4Fe(μ-bmtz)Fe(CN)4]5-/4-/3- (4n) with bmtz=3,6-bis(2-pyrimidyl)-1,2,4,5-tetrazine were studied in acetonitrile and other aprotic solvents. The comproportionation constants Kc for the mixed-valent diiron(III, II) intermediates vary from less than 10 for 35- via 106.5 for 15- to 1014.1 for 43-. Intervalence charge transfer band maxima lie between 1270 nm (25-) and 2475 nm (15-). In comparison with previous results from aqueous solutions, the system 1n in particular shows increased metal-metal interaction. UV-Vis and IR spectroelectrochemistry suggest a localized/delocalized borderline sitation for 15- in acetonitrile, with only slightly weaker metal-metal coupling than in the related Creutz-Taube ion. The results illustrate how the established strong solvent sensitivity of cyanoiron complexes can be exploited in mixed-valence chemistry. © 1999 Elsevier Science S.A. 1999 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201693_v291_n1-2_p66_Ketterle http://hdl.handle.net/20.500.12110/paper_00201693_v291_n1-2_p66_Ketterle
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Cyano complexes
Iron complexes
Mixed-valence complexes
Spectroelectrochemistry
spellingShingle Cyano complexes
Iron complexes
Mixed-valence complexes
Spectroelectrochemistry
Widely differing stabilities of molecule-bridged cyanodiiron(III, II) species in non-aqueous solvents
topic_facet Cyano complexes
Iron complexes
Mixed-valence complexes
Spectroelectrochemistry
description The redox systems [(NC)5Fe(μ-L)Fe(CN)5])6-/5-/4- with L=pyrazine (1n), 4,4′-bipyridine (2n) or 1,2-bis(4-pyridyl)ethene (3n), and [(NC)4Fe(μ-bmtz)Fe(CN)4]5-/4-/3- (4n) with bmtz=3,6-bis(2-pyrimidyl)-1,2,4,5-tetrazine were studied in acetonitrile and other aprotic solvents. The comproportionation constants Kc for the mixed-valent diiron(III, II) intermediates vary from less than 10 for 35- via 106.5 for 15- to 1014.1 for 43-. Intervalence charge transfer band maxima lie between 1270 nm (25-) and 2475 nm (15-). In comparison with previous results from aqueous solutions, the system 1n in particular shows increased metal-metal interaction. UV-Vis and IR spectroelectrochemistry suggest a localized/delocalized borderline sitation for 15- in acetonitrile, with only slightly weaker metal-metal coupling than in the related Creutz-Taube ion. The results illustrate how the established strong solvent sensitivity of cyanoiron complexes can be exploited in mixed-valence chemistry. © 1999 Elsevier Science S.A.
title Widely differing stabilities of molecule-bridged cyanodiiron(III, II) species in non-aqueous solvents
title_short Widely differing stabilities of molecule-bridged cyanodiiron(III, II) species in non-aqueous solvents
title_full Widely differing stabilities of molecule-bridged cyanodiiron(III, II) species in non-aqueous solvents
title_fullStr Widely differing stabilities of molecule-bridged cyanodiiron(III, II) species in non-aqueous solvents
title_full_unstemmed Widely differing stabilities of molecule-bridged cyanodiiron(III, II) species in non-aqueous solvents
title_sort widely differing stabilities of molecule-bridged cyanodiiron(iii, ii) species in non-aqueous solvents
publishDate 1999
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201693_v291_n1-2_p66_Ketterle
http://hdl.handle.net/20.500.12110/paper_00201693_v291_n1-2_p66_Ketterle
_version_ 1768544255497732096

Ejemplares similares