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One possible explanation for the difference in rates relates to the link between the ferrocene and the alkanethiol. Napper et al. (Napper, A. M. L., H. Y.; Waldeck, D. H. J. Phys. Chem. B 2001, 105, 7699.) have shown that the replacement of a methylene by an ether linkage in the alkanethiol reduces the rate of electron transfer by a factor of 4. The link used in the current study is an amide group as part of the bridge, which may influence the coupling between the ferrocene and the bridge, and hence the rate of electron transfer, in a manner similar to an ether linkage. The suggestion that an amide linkage would influence the rate of electron transfer is contrary to the finding of Sumner et al. (Sumner, J. J.; Weber, K. S.; Hockett, L. A.; Creager, S. E. J. Phys. Chem. B 2000, 104, 7449.) where no difference in rate was observed for ferrocene attached directly to an alkane thiol by an amide or a methylene group. Note in the current study the amide group is separated from the ferrocene by a methylene group rather than attached directly to the ferrocene as in the Creager work. As the π-molecular orbitals of the ferrocene extend out into the bridge an amide attached directly to the ferrocene is expected to have a far less significant effect on the electronic coupling, and hence the rate of electron transfer, than an amide a further methylene group away from the redox moiety as in this paper.
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One possible explanation for the difference in rates relates to the link between the ferrocene and the alkanethiol. Napper et al. (Napper, A. M. L., H. Y.; Waldeck, D. H. J. Phys. Chem. B 2001, 105, 7699.) have shown that the replacement of a methylene by an ether linkage in the alkanethiol reduces the rate of electron transfer by a factor of 4. The link used in the current study is an amide group as part of the bridge, which may influence the coupling between the ferrocene and the bridge, and hence the rate of electron transfer, in a manner similar to an ether linkage. The suggestion that an amide linkage would influence the rate of electron transfer is contrary to the finding of Sumner et al. (Sumner, J. J.; Weber, K. S.; Hockett, L. A.; Creager, S. E. J. Phys. Chem. B 2000, 104, 7449.) where no difference in rate was observed for ferrocene attached directly to an alkane thiol by an amide or a methylene group. Note in the current study the amide group is separated from the ferrocene by a methylene group rather than attached directly to the ferrocene as in the Creager work. As the π-molecular orbitals of the ferrocene extend out into the bridge an amide attached directly to the ferrocene is expected to have a far less significant effect on the electronic coupling, and hence the rate of electron transfer, than an amide a further methylene group away from the redox moiety as in this paper.
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