Effects of rapid intramolecular electron transfer on vibrational spectra

Science

Volumn 277, Issue 5326, 1997, Pages 660-663

  Ito, Tasuku ^a   Hamaguchi, Tomohiko ^a   Nagino, Haruko ^a   Yamaguchi, Tadashi ^a   Washington, John ^b   Kubiak, Clifford P ^b  

^a TOHOKU UNIVERSITY   (Japan)

^b PURDUE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON MONOXIDE; CYCLIC VOLTAMMETRY; ELECTROCHEMISTRY; INFRARED SPECTROSCOPY; MOLECULES; RUTHENIUM COMPOUNDS;

RAPID INTRAMOLECULAR ELECTRON TRANSFER;

ELECTRON TRANSPORT PROPERTIES;

ARTICLE; ELECTRON TRANSPORT; INFRARED SPECTROSCOPY; MOLECULAR DYNAMICS; PRIORITY JOURNAL; THERMODYNAMICS; VIBRATION;

EID: 0031214267     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.277.5326.660     Document Type: Article

References (42)

1. G. L. Closs, M. D. Johnson, J. R. Miller, P. Piotrowiak, J. Am. Chem. Soc. 111, 3751 (1989).
2. J. R. Winkler and H. B. Gray, Chem. Rev. 92, 369 (1992).
3. D. Astruc, Electron Transfer and Radical Processes in Transition-Metal Chemistry (VCH, Weinheim, Germany, 1995).
4. C. Creutz and H. Taube, J. Am. Chem. Soc. 91, 3988 (1969).
5. D. E. Richardson and H. Taube, Coord. Chem. Rev. 60, 107 (1984).
6. C. Creutz, Prag. Inorg. Chem. 30, 1 (1983).
7. N. S. Hush, ibid. 8, 391 (1967).
8. N. Sutin, ibid. 30, 441 (1983).
9. J. A. Baumann, D. J. Salmon, S. T. Wilson, T. J. Meyer, Inorg. Chem. 18, 2472 (1979).
10. H. Nagino, thesis, Tohoku University, Sendai, Japan (1995).
11. 3) ppm.
12. M. Abe et al., Inorg. Chem. 35, 6724 (1996).
13. 1/2 corresponds to the difference measured by cyclic voltammetry of the half-wave potentials for the first and second reductions in millivolts (5).
14. J. E. Sutton and H. Taube, Inorg. Chem. 20, 3125 (1981).
15. R. de la Rosa, P. J. Chang, F. Salaymeh, J. C. Curtis, ibid. 24, 4229 (1985).
16. Y. Dong and J. T. Hupp, ibid. 31, 3170 (1992).
17. M. Lacoste et al., J. Am. Chem. Soc. 112, 9548 (1990).
18. The relevant Ru d level is closer to the pyrazine π* level in 1 than it is in 3. This is supported by the following two facts: (i) the metal-to-ligand charge transfer (MLCT) electronic absorption bands for the Ru-d to pyrazine π* transition appear at 482 nm in 1, 475 nm (overlapped) in 2, and 450 nm (overlapped) in 3; and (ii) the reduction potentials become more positive from 1 to 3 (Table 1).
19. -1 for 1 in the fully reduced (-2) state.
20. M. B. Robin and P. Day, Adv. Inorg. Chem. Radiochem. 10, 247 (1967).
21. -1 for 3. Comparison of these values with the experimentally observed data (Table 2) indicates that 1 and 2 are close to fulfilling Robin-Day (20) class III (delocalized) behavior, whereas 3 is clearly class II.
22. IR spectral changes accompanying thin-layer bulk electrolyses were measured with a flow-through spectroelectrochemical cell. Spectroelectrochemical experiments were carried out in 0.1 M tetra-n-butyl ammonium hexafluorophosphate solutions, using freshly distilled tetrahydrofuran or methylene chloride. All solutions were prepared under an atmosphere of nitrogen and degassed completely before injection into the SEC cell. Blank reference solutions containing 0.1 M tetra-n-butyl ammonium hexafluorophosphate were used for the Fourier transform IR solvent subtractions. A Princeton Applied Research (PAR) model 175 Universal Programmer with a PAR model 176 Current Follower were used to effect and monitor thin-layer bulk electrolyses. The IR spectra were acquired with a Mattson Research Series Fourier transform IR equipped with a MCT (mercury-cadmium-telluride) detector.
23. R. E. Wittrig and C. P. Kubiak, J. Eectroanal. Chem. 393, 75 (1995).
24. F.-W. Grevels et al., Angew. Chem. Int. Ed. Engl. 26, 885 (1987).
25. H. L. Strauss, J. Am. Chem. Soc. 114, 905 (1992).
26. J. J. Turner, C. M. Gordon, S. M. Howdle, J. Phys. Chem. 99, 17532 (1995).
27. M. Eigen, Angew. Chem. Int. Ed. Engl. 3, 1 (1964).
28. B. Cohen and S. Weiss, J. Phys. Chem. 87, 3606 (1983).
29. R. A. MacPhail and H. L. Strauss, J. Chem. Phys. 82, 1156 (1985).
30. S. Bratos, G. Tarjus, P. Viot, ibid. 85, 803 (1986).
31. S. Mazur, C. Sreekumar, A. H. Schroeder, J. Am. Chem. Soc. 98, 6713 (1976).
32. A. H. Schroeder and S. Mazur, ibid. 100, 7339 (1978).
33. G. M. Tom and H. Taube, ibid. 97, 5310 (1975).
34. F. Coat and C. Lapinte, Organometallics 15, 477 (1996).
35. R. H. Magnuson and H. Taube, J. Am. Chem. Soc. 94, 7213 (1972).
36. H. Krentzien and H. Taube, ibid. 98, 6379 (1976).
37. M. B. Sponsler, Organometallics 14, 1920 (1995).
38. R. Wu et al., J. Chem. Soc. Chem. Commun. 1994, 1657 (1994).
39. K. A. Wood and H. L. Strauss, J. Phys. Chem. 94, 5677 (1990).
40. A. E. Johnson and A. B. Meyers, ibid. 100, 7778 (1996).
41. IR spectral lineshapes were simulated with the dynamical simulation program VIBEXGL: Program for the Simulation of IR Spectra of Exchanging Systems, made available by R. E. D. McClung, University of Alberta, Alberta, Canada.
42. Supported by NSF grants (CHE-9319173 and CHE-9615886) to C.P.K. and Grants-in-Aid for Scientific Research (08243214 and 09874128) from the Ministry of Education, Science, and Culture and by a grant from Monbusho International Scientific Research Program (No. 09044054) (Japan) to T.I. We also gratefully acknowledge the Japan Society for the Promotion of Science for fellowship support to C.P.K. and Natural Sciences and Engineering Research Council (Canada) for a postdoctoral fellowship to J.W.