Ferrocenyl-terminated redox stars: synthesis and electrostatic effects in mixed-valence stabilization

A family of rigid ferrocenyl-terminated redox stars has been synthesized--by Negishi coupling, including hexa(ferrocenethynyl)benzene complexes, a dodecaferrocenyl star, and stars with extended rigid tethers--and fully characterized. Cyclic voltammetry (CV) studies of the parent complex hexa(ferrocenylethynyl)benzene, 1, show a single wave for the six-electron oxidation of 1 using Nn-Bu(4)PF(6) as the supporting electrolyte on a Pt anode in CH(2)Cl(2), whereas three distinct two-electron reversible CV waves are observed using Nn-Bu(4)BAr(F)(4) (Ar(F) = 3,5-C(6)H(3)-(CF(3))(2)). The CV of 1,3,5-tris(ferrocenylethynyl)benzene, 11, also shows only one wave for the three-electron transfer with Nn-Bu(4)PF(6) and three one-electron waves using Nn-Bu(4)BAr(F)(4). This confirms the lack of electronic communication between the ferrocenyl groups and a significant electrostatic effect among the oxidized ferrocenyl groups. This effect is not significant between para-ferrocenyl groups in 1,4-bis(ferrocenylethynyl)benzene for which only a single wave is observed even with Nn-Bu(4)BAr(F)(4) as the supporting electrolyte. The para-ferrocenyl substituents are quite independent, which explains that two para-ferrocenyl groups are oxidized at about the same potential in a single CV wave of 1. With the additional steric bulk introduced with a methyl substituent on the ferrocenyl group, however, even the para-methylferrocenyl groups are submitted to a small electrostatic effect splitting the six-electron transfer into six single-electron waves, probably because of the overall steroelectronic constraints. Contrary to 11, 1,3-bis(ferrocenylethynyl)benzene and related complexes with a third, different substituent in the remaining meta position different from a ferrocenylethynyl only show a single two-electron wave using Nn-Bu(4)BAr(F)(4), which is attributed to the transoïd conformation of the ferricinium groups minimizing the electrostatic effect. This shows that, in 11, it is the steric frustration that is responsible for the electrostatic effect, and the same occurs in 1. In several cases, ΔE(p) is much larger than the expected 60 mV value, characterizing a quasi-reversible (i.e., relatively slow) redox process. It is suggested that this slower electron transfer be attributed to conformational rearrangement of the ferrocenyl groups toward the transoïd position in the course of electron transfer. Thus both the thermodynamic and kinetic aspects of the electrostatic factor (isolated from the electronic factor), including the frustration effect, are characterized. The distinction between the electronic communication and through-space electrostatic effect was made possible in all of these complexes in which the absence of wave splitting using a strongly ion-pairing electrolyte shows the absence of significant electronic communication, and was confirmed by the new frustration phenomenon.