The FeIII/FeII vs. Fe22.5 Formulation in Mixed-Valent Species (NC)4Fe(BL)Fe(CN)43-, BL = 2,2'-Bipyrimidine and 3,6-Bis(2-pyridyl)-1,2,4,5-tetrazine. Distance and Size Do Not Always Matter
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Inorganic Chemistry 38 (14): 3270--3274 (1999)

Two mol.-bridged bis(tetracyanoiron) complexes (NC)4Fe(BL)Fe(CN)4n-, BL = 2,2'-bipyrimidine (bpym) and 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz), were studied by EPR, UV/visible/near-IR and IR spectroelectrochem. (n = 2-5) in aprotic media. Following these results, the Fe22.5 formulation is the correct valence description for the metal centers in the bptz-bridged trianion (Kc = 1014.6 in MeCN), whereas the localized FeIII/FeII formulation is appropriate for the bpym-bridged system (Kc = 105.4 in MeCN and 106.4 in CH2Cl2). In contrast to common perception, the larger tetrazine-bridged system with the longer metal-metal distance exhibits much stronger metal-metal coupling than the bpym-bridged analog, a consequence of the very low lying p* LUMO of tetrazines with high MO coeffs. at the coordinating N centers. on SciFinder(R)
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