Triplet species from dihydroipyrrolo[3,4-d]pyridazines, the diazene precursors of N-arenesulfonyl-3,4-dimethylenepyrroles

Journal of the American Chemical Society

Volumn 119, Issue 6, 1997, Pages 1416-1427

  Bush, Linda C ^a,b   Maksimovic, Ljiljana ^a   Feng, Xu Wu ^a   Lu, Helen S M ^a   Berson, Jerome A ^a  

^a YALE UNIVERSITY   (United States)

^b SALISBURY UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

PYRIDAZINE DERIVATIVE; PYRROLE DERIVATIVE; PYRROLO[3,4 D]PYRIDAZINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; ELECTRON SPIN RESONANCE; MOLECULAR DYNAMICS; PHOTOCHEMISTRY; QUANTUM CHEMISTRY;

EID: 0030895105     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja963114c     Document Type: Article

References (70)

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40. -1, is large for a radical pair and would require that the radical partners remain close together. Since the same D value is observed in several different matrices, one would have to postulate that, fortuitously, the separation remains the same in all these media. Second, as already has been stated, no such triplet spectra are seen in the photolyses of model compounds such as N-tosylpyrrole or the cycloadducts of biradical 1b and alkenes. Third, to form, in the dark, the observed trapping product 18 from the Lb triplet preparations allegedly containing the 13-14 radical pair would require some such mechanism as thermal deazetation of the radical 14 at 193 K, followed by cycloaddition of the resulting triradical, followed by recombination of the resulting adduct monoradical with radical 13. We consider these joint requirements sufficient to render the radicalpair assignment highly improbable.
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43. For discussions of heavy-atom effects on intersystem crossing, see: (a) McGlynn, S. P.; Azumi, T.; Kinoshita, M. Molecular Spectroscopy of the Triplet State; Prentice-Hall: Englewood Cliffs, NJ, 1969; Chapter 5. (b) Michl, J.; Bonacic-Koutecky, V. Electronic Aspects of Organic Photochemistry; Wiley: New York, 1990; pp 24, 42. (c) Fisher, J. J.; Michl, J. J. Am. Chem. Soc. 1987, 109, 583. (d) Koziar, J. C.; Cowan, D. O. Acc. Chem Res. 1978, 11, 334. (e) Turro, N. J. Modern Molecular Photochemistry; Benjamin-Curamings: New York, 1978; Chapter 6.
44. For discussions of heavy-atom effects on intersystem crossing, see: (a) McGlynn, S. P.; Azumi, T.; Kinoshita, M. Molecular Spectroscopy of the Triplet State; Prentice-Hall: Englewood Cliffs, NJ, 1969; Chapter 5. (b) Michl, J.; Bonacic-Koutecky, V. Electronic Aspects of Organic Photochemistry; Wiley: New York, 1990; pp 24, 42. (c) Fisher, J. J.; Michl, J. J. Am. Chem. Soc. 1987, 109, 583. (d) Koziar, J. C.; Cowan, D. O. Acc. Chem Res. 1978, 11, 334. (e) Turro, N. J. Modern Molecular Photochemistry; Benjamin-Curamings: New York, 1978; Chapter 6.
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