The catalytic reduction of azides and hydrazines using high-valent organouranium complexes [2]

Journal of the American Chemical Society

Volumn 121, Issue 23, 1999, Pages 5585-5586

  Peters, R Gregory ^a   Warner, Benjamin P ^a   Burns, Carol J ^a  

^a LOS ALAMOS NATIONAL LABORATORY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AZIDE; HYDRAZINE DERIVATIVE; OXIDIZING AGENT; URANIUM DERIVATIVE;

CHEMICAL STRUCTURE; COMPLEX FORMATION; LETTER; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; REDUCTION;

EID: 0033575069     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9844581     Document Type: Letter

References (22)

1. Hutchings, G. J.; Heneghan, C. S.; Hudson, I. D.; Taylor, S. H. Nature (London) 1996, 384, 341-343.
2. Haskel, A.; Straub, T.; Eisen, M. S. Organometallics 1996, 15, 3773.
3. Fagan, P. J.; Bowman, R. G.; Nakamura, R.; Burwell, R. L.; Marks, T. J. J. Chem. Soc., Chem Commun. 1981, 6, 257.
4. Campbell, R. E. J. Pentaalkylcyclopentadienyl Actinide Olefin Polymerization Catalysts; Dow Chemical Co.: Midland, MI, 1985.
5. (a) Arney, D. S. J.; Burns, C. J.; Smith, D. C. J. Am. Chem. Soc. 1992, 114, 10068.
6. (b) Warner, B. P.; Scott, B. L.; Burns, C. J. Angew. Chem., Int. Ed. Engl. 1997, 37, 9959.
7. There are several reports of transition metal and actinide imido complexes. (a) Wigley, D. E.; Prog. Inorg. Chem. 1994, 42, 239. (b) Lockwood, M. A.; Fanwick, P. E.; Eisenstein, O.; Rothwell, I. P. J. Am. Chem. Soc. 1996, 118, 2762. (c) Aubart, M. A.; Bergman, R. G. Organometallics 1999, 18, 811. (d) Brennan, J. G.; Andersen, R. A. J. Am. Chem. Soc. 1985, 107, 514.
8. There are several reports of transition metal and actinide imido complexes. (a) Wigley, D. E.; Prog. Inorg. Chem. 1994, 42, 239. (b) Lockwood, M. A.; Fanwick, P. E.; Eisenstein, O.; Rothwell, I. P. J. Am. Chem. Soc. 1996, 118, 2762. (c) Aubart, M. A.; Bergman, R. G. Organometallics 1999, 18, 811. (d) Brennan, J. G.; Andersen, R. A. J. Am. Chem. Soc. 1985, 107, 514.
9. There are several reports of transition metal and actinide imido complexes. (a) Wigley, D. E.; Prog. Inorg. Chem. 1994, 42, 239. (b) Lockwood, M. A.; Fanwick, P. E.; Eisenstein, O.; Rothwell, I. P. J. Am. Chem. Soc. 1996, 118, 2762. (c) Aubart, M. A.; Bergman, R. G. Organometallics 1999, 18, 811. (d) Brennan, J. G.; Andersen, R. A. J. Am. Chem. Soc. 1985, 107, 514.
10. There are several reports of transition metal and actinide imido complexes. (a) Wigley, D. E.; Prog. Inorg. Chem. 1994, 42, 239. (b) Lockwood, M. A.; Fanwick, P. E.; Eisenstein, O.; Rothwell, I. P. J. Am. Chem. Soc. 1996, 118, 2762. (c) Aubart, M. A.; Bergman, R. G. Organometallics 1999, 18, 811. (d) Brennan, J. G.; Andersen, R. A. J. Am. Chem. Soc. 1985, 107, 514.
11. 2U(Cl)(NaCl) was prepared according to an established literature procedure: Fagan, P. J.; Manriquez, J. M.; Marks, T. J.; Day, C. S.; Vollmer, S. H.; Day, V. W. Organometallics 1982, 1, 170.
12. Arney, D. S. J.; Burns, C. J. J. Am. Chem. Soc. 1995, 117, 9448.
13. 2. The reaction was complete after 24 h.
14. 2U: C, 59.39; H, 7.73; N, 3.46. Found: C, 59.08; H, 7.48; N, 3.40.
15. 6 (0.7 mL). The reaction was monitored by NMR and found to be complete and quantitative after 3 h.
16. 2 (0.160 g, 1.06 mmol, 76%) was purified by flash chromatography.
17. Nakamura, A.; Aotake, M.; Otsuka, S. J. Am. Chem. Soc. 1974, 96, 3456.
18. 2O to yield azobenzene (0.235 g, 1.29 mmol, quantitative).
19. Both stoichiometric oxidation and reduction steps were examined. While the reaction of 3 plus hydrazine can be observed directly and results in the formation of aniline and 1, formation of 3 by reduction of 1 with N,N′-diphenylhydrazine cannot be directly observed; only 1 is present in detectable quantities throughout the course of the reaction, suggesting that the oxidation of 3 to 1 is faster than the reduction of 1 to 3.
20. Cole, L. G.; Gilbert, E. C. J. Am. Chem. Soc. 1951, 73, 5423.
21. 6 (0.6 mL). After 42 h at room temperature, all of the N,N′-diphenylhydrazine starting material had been consumed. The only organic products observed by NMR were aniline and azobenzene in a 2:1 ratio. Compound 2 was the only uranium-containing compound observed in solution.
22. An explanation of f orbitals and their role in the bonding and reactivity of U(VI) complexes is provided in ref 5b.