Electrophilic aromatic nitrosation. Isolation and X-ray crystallography of the metastable NO+ complex with nitrosoarene

Journal of the Chemical Society. Perkin Transactions 2

Volumn , Issue 9, 2000, Pages 1919-1923

  Lindeman, Sergey V ^a   Bosch, Eric ^a   Kochi, Jay K ^a  

^a University of Houston   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHARGE TRANSFER; ELECTRONIC PROPERTIES; HYDROGEN BONDS; MOLECULAR STRUCTURE; NEGATIVE IONS; PASSIVATION; POSITIVE IONS; SINGLE CRYSTALS; TITRATION; X RAY CRYSTALLOGRAPHY;

CHARGE DISTRIBUTION; ELECTROPHILIC AROMATIC NITROSATION; NITROSOARENE;

NITROGEN COMPOUNDS;

EID: 0034286438     PISSN: 03009580     EISSN: None     Source Type: Journal    
DOI: 10.1039/b002686g     Document Type: Article

References (42)

1. R. Taylor, Electrophilic Aromatic Substitution, Wiley, New York, 1990.
2. B. C. Challis, R. J. Higgins and A. J. Lawson, J. Chem. Soc., Perkin Trans. 2, 1973, 1597
3. L. R. Dix and R. B. Moodie, J. Chem. Soc., Perkin Trans. 2, 1968, 1097
4. V. L. Lobachev, E. S. Rudakov and O. B. Savunenko, Kinet. Catal., 1990, 31, 680 and references therein.
5. E. Bosch and J. K. Kochi, J. Org. Chem., 1994, 59, 5573.
6. J. H. Atherton, R. B. Moodie and D. R. Noble, J. Chem. Soc., Perkin Trans. 2, 2000, 229.
7. O. Drangfelt and C. Römming, Acta Chem. Scand., Ser. A, 1974, 28, 1101.
8. S. Hu, D. M. Thompson, P. O. Ikekwere, R. J. Barton, K. E. Johnson and B. E. Robertson, Inorg. Chem., 1989, 28, 4552
9. N. G. Bokii, A. I. Udel'nov, Yu. T. Struchkov, D. N. Kravtsov and V. M. Pacherskaya, Zh. Strukt. Khim., 1977, 18, 1025
10. S. J. Fox, L. Chen, M. A. Khan and G. B. Richter-Addo, Inorg. Chem., 1997, 36, 6465.
11. 2 and OH groups). By contrast, a closely related nitro group is known as a very poor proton acceptor.
12. R. G. Pritchard, G. S. Heaton and I. M. El-Nahhal, Acta Crystallogr., Sect. C, 1989, 45, 829.
13. H. J. Talberg, Acta Chem. Scand., Ser. A, 1975, 29, 919.
14. J. H. Atherton, R. B. Moodie and D. R. Noble, J. Chem. Soc., Perkin Trans. 2, 1999, 699.
15. F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen and R. Taylor, J. Chem. Soc., Perkin Trans. 2, 1987, S1.
16. A. Bondi, J. Phys. Chem., 1964, 68, 441.
17. L. Pauling, The Nature of the Chemical Bond, Cornell University Press, Ithaca, NY, 1960, p. 280.
18. H. J. Talberg, Acta Chem. Scand., Ser. A, 1979, 33, 289.
19. T. Mori, S. V. Lindeman and J. K. Kochi, Electronic submission to the Cambridge Crystallographic Database No. 138882, 2000.
20. E. K. Kim and J. K. Kochi, J. Org. Chem., 1993, 58, 786.
21. + as a "soft" π-acceptor with aromatic donors, see E. K. Kim and J. K. Kochi, J. Am. Chem. Soc., 1991, 113, 4962.
22. The prototypical nitric oxide and nitrosomethane, as described by W. L. Jorgensen and L. Salem (The Organic Chemist's Book of Orbitals, Academic Press, New York, 1973, pp. 80 and 149-150), were used for an orbital description.
23. In most nitrosoarenes, this angle is less than 120° owing to orbital repulsion with the n-electron pair of the nitrogen atom.
24. For example, this bond is 1.368 Å in N,N-dimethyl-4-nitrosoaniline; see K. Lewinski W. Nitek and P. Milart, Acta Crystallogr., Sect. C, 1993, 49, 188. Crystallographic data on 4-nitrosoanisole itself do not provide a confident value because of a structural disorder (ref. 14).
25. 14
26. For a quantitative description of quinoidal distortions in aromatic cations, see R. Rathore, S. V. Lindeman, A. S. Kumar and J. K. Kochi, J. Am. Chem. Soc., 1998, 120, 6931.
27. The C-OMe bond length is reduced to 1.320(4) Å in 1 as compared with 1.335(4) Å in the uncomplexed molecule (ref.14).
28. 14 is also in line with this argument.
29. The rotation is presumbly around the C(Ar)-NO bond in 1 but it may be more complex.
30. J. A. Hirsch, Concepts in Theoretical Organic Chemistry, Allyn and Bacon, Boston, 1974, pp. 99-102.
31. D. L. Huges and J. Trotter, J. Chem. Soc. A, 1971, 2181 and references therein.
32. From the structure of p-benzoquinone 4-oxime; see H. J. Talberg, Acta Chem. Scand., Ser. A, 1974, 28, 910.
33. K. R. Rowan and E. M. Holt, Acta Crystallogr., Sect. C, 1995, 51, 2554.
34. R. Boese D. Blaser, M. Nussbaumer and T. M. Krygovski, Struct. Chem., 1992, 3, 363.
35. Average data over four structures; see Y. Mazaki and K. Mutai, Bull. Chem. Soc. Jpn., 1995, 68, 3247.
36. M. C. Etter, Z. Urbanczyk-Lipkowska, M. Zia-Ebrahimi and T. W. Panunto, J. Am. Chem. Soc., 1990, 112, 8415.
37. 2+ salts; see H. J. Talberg, Acta Chem. Scand., Ser. A, 1975, 29, 919
38. H. J. Talberg, Acta Chem. Scand., Ser. A, 1977, 31, 37.
39. + salt; see E. K. Andersen, I. G. K. Andersen and G. Ploug-Sorensen, Acta Chem. Scand., 1989, 43, 624.
40. p = 0.78 for the nitro substituent) is accepted.
41. 2 results from its enchanced resonance effect; see C. Hansch, A. Leo and R. W. Taft, Chem. Rev., 1991, 91, 165.
42. G. M. Sheldrick, SHELXTL, Bruker Analytical X-Ray Systems, Madison, Wisconsin, USA, 1997.