Long range charge transfer in trimetallic mixed-valence iron complexes mediated by redox non-innocent cyanoacetylide ligands.

The reaction of Fe(C≡CC≡N)(dppe)Cp (1) with one-half equivalent of [trans-Fe(N≡CMe)2(dppx)2][BF4]2 (dppx = dppe ([2][BF4]2) or dppm ([3][BF4]2)) affords trimetallic [trans-Fe{N≡CC≡CFe(dppe)Cp}2(dppx)2][BF4]2 (dppx = dppe [4][BF4]2; dppx = dppm [5][BF4]2). Both [4][BF4]2 and [5][BF4]2 undergo three, one-electron oxidation processes, arising from sequential oxidation of the two terminal Fe(C≡CR)(dppe)Cp moieties and finally the central Fe(N≡CR)2(dppx)2 fragment. The redox products [4](n+) and [5](n+) (n = 3, 4) have been characterised by UV-vis-NIR and IR spectroelectrochemistry.