Solution phase and single crystal diffraction X-ray analyses of diprotonated porphyrin isomers - Etioporphyrin, etioporphycene, and etiocorrphycene bishydroperchlorate salts

Chemistry - A European Journal

Volumn 2, Issue 12, 1996, Pages 1527-1532

  Sessler, Jonathan L ^a   Brucker, Eric A ^a   Lynch, Vincent ^a   Choe, Michael ^a   Sorey, Steven ^a   Vogel, Emanuel ^b  

^a UNIVERSITY OF TEXAS AT AUSTIN   (United States)

^b UNIVERSITY OF COLOGNE   (Germany)

Author keywords

Corrphycenes; Porphycenes; Porphyrinoids; Protonations; Structure elucidation

Indexed keywords

CORRPHYCENES; PORPHYCENES; PORPHYRINOIDS; PROTONATIONS; STRUCTURE ELUCIDATION;

DICHLOROMETHANE; HYDROGEN BONDS; INORGANIC COMPOUNDS; ISOMERS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PORPHYRINS; PROTONS; SALTS; X RAY DIFFRACTION; X RAY DIFFRACTION ANALYSIS;

PROTONATION;

EID: 0000584277     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.19960021209     Document Type: Article

References (44)

1. Porphyrin Isomers: a) J. L. Sessler, Angew. Chem. Int. Ed. Engl. 1994, 33, 1348-1350.
2. Porphycenes: b) E. Vogel, M. Köcher, H. Schmickler, J. Lex, ibid. 1986, 25, 257-259.
3. c) E. Vogel, M. Balei, K. Pramod, P. Koch, J. Lex, O. Ermer, ibid. 1987, 26, 928-931.
4. d) B. Wehrle, H.-H. Limbach, M. Köcher, O. Ermer, E. Vogel, ibid. 1987, 26, 934-936.
5. e) E. Vogel, Pure Appl. Chem. 1990, 62, 557-564.
6. f) E. Vogel, P. Koch, X.-L. Hou, J. Lex, M. Lausmann, M. Kisters, M. A. Aukauloo, P. Richard, R. Guilard, Angew. Chem. Int. Ed. Engl. 1993, 32, 1600-1604.
7. Corrphycenes: g) J. L. Sessler, E. A. Brucker, S. J. Weghorn, M. Kisters, M. Schäfer, J. Lex, E. Vogel, ibid. 1994, 33, 2308-2312.
8. h) M. A. Aukauloo, R. Guilard, New J. Chem. 1994, 18, 1205-1207.
9. i) H. Falk, Q.-Q. Chen, R. Micura, Monatssh. Chem. 1996, 127, 77-83.
10. Metallocorrphycenes: j) E. Vogel, J. L. Sessler, unpublished results.
11. Hemiporphycenes: k) H. Callot, New J. Chem. 1995, 19, 155-159.
12. l) E. Vogel, J. L. Sessler, unpublished results.
13. N-confused (inverted) porphyrins: m) H. Furuta, T. Asano, T. Ogawa, J. Am. Chem. Soc. 1994, 116, 767-768.
14. n) P. J. Chielewski, L. Latos-Grazynski, K. Rachlewicz, T. Glowiak, Angew. Chem. Int. Ed. Engl. 1994, 33, 779-781.
15. In recent, as yet unpublished work, the structure of a third pyrrole-in free-base porphyrin isomer, hemiporphycene, has been solved [11]. This same isomer has been characterized structurally as its nickel(II) complex [1 k].
16. 13,16] tetracosa-1(20),2(21),3,5,7,9,11,13(23),14,16,18-undecene (etiocorrphycene), respectively.
17. This porphyrin was synthesized according to the procedure of H. L. Anderson, J. K. M. Sanders, Angew. Chem. Int. Ed. Engl. 1990, 29, 1400-1403, but with formaldehyde replacing the benzaldehyde derivative originally used.
18. w(F) = 0.0866, and goodness of fit = 2.047 for 441 parameters.
19. w(F) = 0.0500, and goodness of fit = 1.22 for 277 parameters.
20. w(F) = 0.0988, and goodness of fit = 0.86 for 415 parameters.
21. Etioporphyrin II is structurally equivalent to octaethylporphyrin, whose X-ray structure has been solved: J. W. Lauher, J. A. Ibers, J. Am. Chem. Soc. 1973, 95, 5148-5152.
22. S. C. Wallwork, Acta Crystallogr. 1962, 15, 758-759.
23. a) C. P. Hrung, M. Tsutsui, D. L. Cullen, E. F. Meyer, J. Am. Chem. Soc. 1976, 98, 7878-7880.
24. b) N. Hirayama, A. Takenaka, Y. Sasada, E.-I. Watanabe, H. Ogoshi, Z.-I. Yoshida, J. Chem. Soc. Chem. Commun. 1974, 330-331.
25. -, the only other diprotonated octaalkylporphyrin of whose structure we are aware [12], the porphyrin dication was found to be essentially planar. This establishes that the oft-discussed [10b,13] destabilizing H⋯H nonbonded interactions, presumed to occur within the core of diprotonated porphyrins, need not necessarily give rise to deviations from planarity, even though this often [10,13] appears to be the case.
26. E. Cetinkaya, A. W. Johnson, M. F. Lappert, G. M. McLaughlin, K. W. Muir, J. Chem. Soc. Dalton Trans. 1974, 1236-1243.
27. a) E. B. Fleischer, Acc. Chem. Res. 1970, 3, 105-112.
28. b) A. Stone, E. B. Fleischer, J. Am. Chem. Soc. 1968, 90, 2735-2748.
29. c) E. B. Fleischer, A. L. Stone, J. Chem. Soc. Chem. Commun. 1967, 332-333.
30. 4 so as to maintain a congruence between these extraction experiments and the X-ray diffraction ones carried out in the solid state.
31. a units. Nonetheless, in the present instance, such an extraction-based approach should permit meaningful comparisons between isomers.
32. H. Furuta, M. J. Cyr, J. L. Sessler, J. Am. Chem. Soc. 1991, 113, 6677-6678.
33. V. Král, H. Furuta, K. Shreder, V. Lynch, J. L. Sessler, J. Am. Chem. Soc. 1996, 118, 1595-1607.
34. In the case of porphycene and corrphycene, two tautomeric forms can be considered for the proposed monoprotonated intermediates. However, in the present study no direct information about these states was obtained. Certainly, in the case of porphyrin per se, observation of the porphyrin monocation is generally considered to be difficult (see: Porphyrins and Metalloporphyrins (Ed.: K. M. Smith), Elsevier, Amsterdam: 1975, pp. 11-13). Such species, however, have been isolated and characterized in the solid state; see ref. [10].
35. 2: δ = -3.74 (s, 2H, NH), -3.01 (s, 2H, NH), 1.75 (t, 6H, ethyl), 1.78 (t, 6H, ethyl), 3.48 (s, 6H, methyl), 3.64 (s, 6H, methyl), 3.95 (q, 4H, ethyl), 4.05 (q, 4H, ethyl), 10.30 (s, 2H, meso), 10.54 (s, 2H, meso).
36. a) C. S. Irving, A. Lapidot, J. Chem. Soc. Chem. Commun. 1977, 184-186.
37. b) M. Schlabach, B. Wehrle, H. Rumpel, J. Braun, G. Scherer, H. H. Limbach, Ber. Bunsenges. Phys. Chem. 1992, 96, 821-833.
38. c) M. Schlabach, H. H. Limbach, E. Bunnenberg, A. Y. L. Shu, B. R. Tolt, C. Djerassi, J. Am. Chem. Soc. 1993, 115, 4554-4570.
39. a) M. Schlabach, G. Scherer, H. H. Limbach, J. Am. Chem. Soc. 1991, 113, 3550-3558.
40. b) R. Bonnett, B. D. Djelal, G. E. Hawkes, P. Haycock, F. Pont, J. Chem. Soc. Perkin Trans 2 1994, 1839-1843.
41. D. Gust, J. D. Roberts, J. Am. Chem. Soc. 1977, 99, 3637-3640.
42. a) C. B. Storm, Y. Teklu, J. Am. Chem. Soc. 1972, 94, 1745-1747.
43. b) R. J. Abraham, G. E. Hawkes, K. M. Smith Tetrahedron Lett. 1974, 1483-1486.
44. Ref. [18], p. 873.