Widely differing stabilities of molecule-bridged cyanodiiron(III,II) species in non-aqueous solvents
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Inorganica Chimica Acta 291 (1-2): 66--73 (1999)

The redox systems (NC)5Fe(m-L)Fe(CN)56-/5-/4- with L = pyrazine (1n), 4,4'-bipyridine (2n) or 1,2-bis(4-pyridyl)ethene (3n), and (NC)4Fe(m-bmtz)Fe(CN)45-/4-/3- (4n) with bmtz = 3,6-bis(2-pyrimidyl)-1,2,4,5-tetrazine were studied in MeCN and other aprotic solvents. The comproportionation consts. Kc for the mixed-valent diiron(III, II) intermediates vary from \textless10 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 aq. solns., the system 1n in particular shows increased metal-metal interaction. UV-visible and IR spectroelectrochem. suggest a localized/delocalized borderline situation for 15- in MeCN, with only slightly weaker metal-metal coupling than in the related Creutz-Taube ion. The established strong solvent sensitivity of cyanoiron complexes can be exploited in mixed-valence chem. on SciFinder(R)
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