Intramolecular electron transfer between doubly six σ-bond-linked trialkyldiazenium cation and diazenyl radical units

Journal of the American Chemical Society

Volumn 119, Issue 29, 1997, Pages 6873-6882

  Nelsen, Stephen F ^a   Trieber II, Dwight A ^a   Wolff, J Jens ^a   Powell, Douglas R ^a   Rogers Crowley, Shervalen ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

2 TERT BUTYL 2,3 DIAZABICYCLO[2.2.2]OCTYLDIAZENIUM; ACETONITRILE; CATION; HYDRAZINE DERIVATIVE; N,N DIMETHYLFORMAMIDE; UNCLASSIFIED DRUG;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CRYSTAL STRUCTURE; CYCLIC POTENTIOMETRY; DIASTEREOISOMER; ELECTRON SPIN RESONANCE; ELECTRON TRANSPORT; ENERGY; SIMULATION; TEMPERATURE; THEORY;

EID: 0030822889     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9634177     Document Type: Article

References (32)

1. For a review of mixed-valence complexes, see: Creutz, C. Prog. Inorg. Chem. 1983, 30, 1.
2. (a) Nelsen, S. F.; Chang, H.; Wolff, J. J.; Adamus, J. J. Am. Chem. Soc. 1993, 115, 12276.
3. (b) Nelsen, S. F.; Chang, H.; Powell, D. R. J. Org. Chem. 1994, 59, 6558.
4. Dovlaitzky, M.; Chiarelli, R.; Rassat, R. Angew. Chem. Int. Ed. Engl. 1992, 31, 180. They quote Hirota (Hirota, N., Weissman, S. I. J. Am. Chem. Soc. 1964, 86, 1538) as the source of the formula, although what is given there is the Hamiltonian used to derive it.
5. Dovlaitzky, M.; Chiarelli, R.; Rassat, R. Angew. Chem. Int. Ed. Engl. 1992, 31, 180. They quote Hirota (Hirota, N., Weissman, S. I. J. Am. Chem. Soc. 1964, 86, 1538) as the source of the formula, although what is given there is the Hamiltonian used to derive it.
6. Nelsen, S. F.; Echegoyen, L. J. Am. Chem. Soc. 1975, 97, 4930.
7. The x,y plane bisects the N=N bonds, the y direction is parallel to the longer axis, and the z direction is parallel to the N=N bonds.
8. (a) Shepard, M. J.; Paddon-Row, M. N.; Jordan, K. D. J. Am. Chem. Soc. 1994, 116, 5328.
9. (b) Jordan, K. D.; Paddon-Row, M. N. Chem. Rev. 1992, 92, 395.
10. + significantly too large at 0.63 kcal/mol (AM1) and 0.68 kcal/mol (PM3).
11. Young, R. H. J. Chem. Phys. 1992, 97, 8261.
12. v is predicted to be exceptionally sensitive to this difference.
13. (b) Nelsen, S. F. J. Am. Chem. Soc. 1996, 118, 2047.
14. (a) Nelsen, S. F.; Ramm, M. T.; Wolff, J. J.; Powell, D. R. J. Am. Chem. Soc. 1997, 119, xxxx.
15. (b) See ref 13a, footnote 14.
16. 13a
17. Oevering, H.; Paddon-Row, M. N.; Heppener, M.; Oliver, A. M.; Cotsaris, E.; Verhoeven, J. W.; Hush, N. S. J. Am. Chem. Soc. 1987, 109, 3285.
18. Bixon, M.; Jortner, J.; Verhoeven, J. W. J. Am. Chem. Soc. 1994, 116, 7349.
19. Ulstrup, J.; Jortner, J. J. Chem. Phys. 1975, 63, 4358.
20. Gould, I. R.; Noukakis, D.; Gomez-Jahn, L.; Young, R. H.; Goodman, J. L.; Farid, S. Chem. Phys. 1993, 176, 439.
21. R. Williams, J. T. Hupp, M. T. Ramm, and S. F. Nelsen, unpublished results.
22. ESR values.
23. s.
24. MacKenzie, K. J. Am. Chem. Soc. 1960, 82, 473.
25. (a) Sheldrick, G. M. Acta Crystallogr. 1990, A46, 467.
26. (b) Sheldrick, G. M. Manuscript in preparation.
27. (c) Neutral atom scattering factors were taken from International Tables for Crystallography; Kluwer:Boston, 1992; Vol. C, Tables 6.1.1.4, 4.2.6.8, 4.2.4.2.
28. (d) SHELXTL version 5 Reference Manual, Siemens Analytical X-ray Instruments, 6300 Enterprise Dr., Madison, WI 53719-1173.
29. The authors have deposited atomic coordinates for this structure with the Cambridge Crystallographic Data Centre. The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, U.K.
30. (a) For AM1, see: Dewar, M. J. S.; Zoebisch, E. G.; Healey, E. F.; Stewart, J. J. P. J. Am. Chem. Soc. 1985, 107, 3902.
31. (b) For MNDO-PM3, see: Stewart, J. J. P. J. Comput. Chem. 1989, 10, 221.
32. VAMP calculations used version 5.6 (on an IBM RS-6000). See: Rauhut, G.; Chandrasekhar, J.; Alex, A.; Steinke, T.; Clark, T. VAMP 5.0, Oxford Molecular: Oxford, 1994.