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...
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| Acceso en línea: | http://hdl.handle.net/20.500.12110/paper_00201693_v291_n1-2_p66_Ketterle |
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todo:paper_00201693_v291_n1-2_p66_Ketterle2023-10-03T14:17:15Z Widely differing stabilities of molecule-bridged cyanodiiron(III, II) species in non-aqueous solvents Ketterle, M. Kaim, W. Olabe, J.A. Parise, A.R. Fiedler, J. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar 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 |
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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 Ketterle, M. Kaim, W. Olabe, J.A. Parise, A.R. Fiedler, J. 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. |
| format |
JOUR |
| author |
Ketterle, M. Kaim, W. Olabe, J.A. Parise, A.R. Fiedler, J. |
| author_facet |
Ketterle, M. Kaim, W. Olabe, J.A. Parise, A.R. Fiedler, J. |
| author_sort |
Ketterle, M. |
| 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 |
| url |
http://hdl.handle.net/20.500.12110/paper_00201693_v291_n1-2_p66_Ketterle |
| work_keys_str_mv |
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1807321653434122240 |