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• W2951996521 abstract "The effects on the rate of electron transfer of replacing 1,by Br21in the mixed-valence compounds It,6’-diiodobiferrocenium triiodide (3), 1’,6’-dibromobiferrocenium triiodide (4), and 1’,6’-dichlorobiferrocenium triiodide (2) are examined. Replacing I,by Br21in the first two complexes leads to an appreciable decrease in the rate of electron transfer, whereas in the case of the third complex an increase in the rate is seen. The triiodide complex 3 shows a single “average-valence” 57Fe Mossbauer doublet at 4.2 K; that is, the electron-transfer rate is in excess of lo7 s-l at 4.2 K. Two doublets are seen at 4.2 K for 1’,6’-diiodobiferrocenium dibromoiodate (9). It is necessary to heat 9 to -80 K so that the rate exceeds I O 7 s-I. Two Mossbauer doublets are also seen at 4.2 K for 1’,6’-dibromobiferrocenium dibromoiodate (lo), whereas 4 shows one doublet. The mixed-valence complex 10 needs to be heated to -180 K to have the rate be in excess of lo7 s-’. Complex 2 is Mossbauer-localized up to -340 K; however replacing the I,by Br21to give 8 changes this such that 8 begins to show some Mossbauer-delocalized species at 100 K, and at 300 K there are approximately equal amounts of Mossbauer-localized and -delocalized species present. This increase in rate by replacing I,by Br21is what was seen before for biferrocenium triiodide (1). A qualitative model is presented to explain these anion effects on the intramolecular electron-transfer rate of mixed-valence biferrocenes. It is shown that the difference in response of I< replacement by Br21reflects the different packing arrangements in the solid state. The Occurrence of a phase transition is strongly indicated. In 1 there are stacks of mixed-valence cations, and cation-cation interactions are important. The greater electron-transfer rate in biferrocenium dibromoiodate than in biferrocenium triiodide could be a reflection of three possibilities: 1, charge oscillation between two asymmetric forms of the trihalide anion is easier in Br21than in I<; 2, the Br21ion begins to move between two lattice positions at lower temperatures than the 1,anion; and 3, the replacement of 1,by BrJ reduces the intrastack cation-cation interactions which lead to valence trapping. The packing arrangement in 3, 4, 9, and 10 is comprised of alternating stacks of cations and anions. Unlike the situation for 1, IR and EPR results for these complexes show that the mixed-valence cation is appreciably influenced by changing the anion. The origin of this is the appreciable in-stack interaction between the terminal atom of the trihalide anion and the iodine atom on the cyclopentadienyl ring. Thus, changing Ijin 3 to give the Br21salt 9 leads to an increase in the in-stack cation-anion interaction, and a higher temperature is needed for 9 to achieve an electron-transfer rate in excess of I O 7 s-l. In the last year or two there has been considerable progress made in understanding what factors control the rate of intramolecular electron transfer in the solid state for mixed-valence biferrocenes”’ and oxo-centered trinuclear iron acetates.’-I2 The ( I ) O n sabbatical leave from the Department of Engineering Physics, The University of Electro-Communications, Chofu, Tokyo 182, Japan. (2) Dong, T-Y.; Cohn, M. J.; Hendrickson, D. N.; Pierpont, C. G. J. Am. Chem. SOC. 1985, 107, 4171. (3) Cohn, M. J.; Dong, T.-Y.; Hendrickson, D. N.; Geib, S. J.; Rheingold, A. L. J . Chem. SOC., Chem. Commun. 1985, 1095. (4) Dong, T.-Y.; Hendrickson, D. N.; Iwai, K.; Cohn, M. J.; Rheingold, A. L.; Sano, H.; Motoyama, I.; Nakashima, S . J . Am. Chem. Soc. 1985, 107, 1996. (5) Dong, T.-Y.; Hendrickson, D. N.; Pierpont, C. G.; Moore, M. F. J. Am. Chem. SOC. 1986, 108, 963. (6) Moore, M. F.; Wilson, S. R.; Cohn, M. J.; Dong, T.-Y.; MuellerWesterhoff, U. T.; Hendrickson, D. N. Inorg. Chem. 1985, 24, 4559. (7) Hendrickson, D. N.; Oh, S. M.; Dong, T.-Y.; Kambara, T.; Cohn, M. J.; Moore, M. F. Comm. Inorg. Chem. 1985, 4 , 329. (8) (a) Oh, S. M.; Hendrickson, D. N.; Hassett, K. L.; Davis, R. E. J . Am. Chem. SOC. 1984, 106,1984. (b) Oh, S. M.; Hendrickson, D. N.; Hassett, K. L.; Davis, R. E. J . Am. Chem. SOC. 1985, 107, 8009. (9) Oh, S. M.; Kambara, T.; Hendrickson, D. N.; Sorai, M.; Kaji, K.; Woehler, S. E; Wittebort, R. J . J . Am. Chem. SOC. 1985, 107, 5540. (10). Kambara, T.; Hendrickson, D. N.; Sorai, M.; Oh, S . M. J. Chem. Phys., in press. exact positioning of a counterion, a ligand, or even a solvate molecule relative to the mixed-valence complex in the solid state can have a dramatic impact on the rate of intramolecular electron transfer. When there is an onset of dynamics associated with the c o ~ n t e r i o n , ~ , ~ ligand,7s8 or solvate molecule~~”J2 this probably will influence the rate of intramolecular electron transfer. In fact, because there are interactions between molecules in the solid state, frequently changes in the rate of intramolecular electron transfer are coupled to phase transition^.^*^^^^-' Mixed-valence compound 2 crystallizes with half a mole of 12. The X-ray structure’ of this compound shows that not only is the I,anion asymmetric but the 1,counterion sits closer to one half of the cation, the iron(II1) metallocene moiety. As a result, mixed-valence compound 2 is localized on the Mossbauer time scale even a t 340 K.5si3 The ground-state double-well potential-energy surface for the mixed-valence cation in 2 is asymmetric (11) Sorai, M.; Kaji, M.; Hendrickson, D. N.; Oh, S. M . J. A m . Chem. (12) Woehler, S. E.; Wittebort, R. J . ; Oh, S. M.; Hendrickson, D. N.; (13) Motoyama, I . ; Suto, K.; Katada, M.; Sano, H. Chem. Lett. 1983, SOC. 1986, 108. 702. Inniss, D.; Strouse, C. E. J. Am. Chem. SOC. 1986, 108, 2938." @default.
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• W2951996521 title "ChemInform Abstract: Mixed-Valence 1′,6′-Dihalobiferrocenium Cations: Counterions Micromodulating Intramolecular Electron Transfer." @default.
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