Octaethyltetraselenaporphyrin dication

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 23, 1997, Pages 2609-2612

  Vogel, Emanuel ^a   Fröde, Christoph ^a   Breihan, Andreas ^b   Schmickler, Hans ^a   Lex, Johann ^a  

^a UNIVERSITY OF COLOGNE   (Germany)

^b NONE

Author keywords

Aromaticity; Heterocycles; Macrocycles; Porphyrinoids; Selenium

Indexed keywords

EID: 0031574005     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199726091     Document Type: Article

References (48)

1. E. Vogel, W. Haas, B. Knipp. J. Lex, H. Schmickler, Angew. Chem. 1988, 100, 445; Angew: Chem. Int. Ed. Engl. 1988, 27, 406; W. Haas, B. Knipp, M. Sicken, J. Lex, E. Vogel, ibid. 1988, 100, 448 and 1988, 27, 409; for expanded tetraoxaporphyrin dicalions see: G. Märkl, H. Sauer, P. Kreitmeier, T. Burgemeister, F. Kastner, G. Adolin, H. Nöth, K. Polborn, ibid. 1994, 106, 1211 and 1994, 33, 1151; R. Bachmann, F. Gerson, C. Pütz, E. Vogel, J. Chem. Soc. Perkin Trans. 2, 1996, 541.
2. E. Vogel, W. Haas, B. Knipp. J. Lex, H. Schmickler, Angew. Chem. 1988, 100, 445; Angew: Chem. Int. Ed. Engl. 1988, 27, 406; W. Haas, B. Knipp, M. Sicken, J. Lex, E. Vogel, ibid. 1988, 100, 448 and 1988, 27, 409; for expanded tetraoxaporphyrin dicalions see: G. Märkl, H. Sauer, P. Kreitmeier, T. Burgemeister, F. Kastner, G. Adolin, H. Nöth, K. Polborn, ibid. 1994, 106, 1211 and 1994, 33, 1151; R. Bachmann, F. Gerson, C. Pütz, E. Vogel, J. Chem. Soc. Perkin Trans. 2, 1996, 541.
3. E. Vogel, W. Haas, B. Knipp. J. Lex, H. Schmickler, Angew. Chem. 1988, 100, 445; Angew: Chem. Int. Ed. Engl. 1988, 27, 406; W. Haas, B. Knipp, M. Sicken, J. Lex, E. Vogel, ibid. 1988, 100, 448 and 1988, 27, 409; for expanded tetraoxaporphyrin dicalions see: G. Märkl, H. Sauer, P. Kreitmeier, T. Burgemeister, F. Kastner, G. Adolin, H. Nöth, K. Polborn, ibid. 1994, 106, 1211 and 1994, 33, 1151; R. Bachmann, F. Gerson, C. Pütz, E. Vogel, J. Chem. Soc. Perkin Trans. 2, 1996, 541.
4. E. Vogel, W. Haas, B. Knipp. J. Lex, H. Schmickler, Angew. Chem. 1988, 100, 445; Angew: Chem. Int. Ed. Engl. 1988, 27, 406; W. Haas, B. Knipp, M. Sicken, J. Lex, E. Vogel, ibid. 1988, 100, 448 and 1988, 27, 409; for expanded tetraoxaporphyrin dicalions see: G. Märkl, H. Sauer, P. Kreitmeier, T. Burgemeister, F. Kastner, G. Adolin, H. Nöth, K. Polborn, ibid. 1994, 106, 1211 and 1994, 33, 1151; R. Bachmann, F. Gerson, C. Pütz, E. Vogel, J. Chem. Soc. Perkin Trans. 2, 1996, 541.
5. E. Vogel, W. Haas, B. Knipp. J. Lex, H. Schmickler, Angew. Chem. 1988, 100, 445; Angew: Chem. Int. Ed. Engl. 1988, 27, 406; W. Haas, B. Knipp, M. Sicken, J. Lex, E. Vogel, ibid. 1988, 100, 448 and 1988, 27, 409; for expanded tetraoxaporphyrin dicalions see: G. Märkl, H. Sauer, P. Kreitmeier, T. Burgemeister, F. Kastner, G. Adolin, H. Nöth, K. Polborn, ibid. 1994, 106, 1211 and 1994, 33, 1151; R. Bachmann, F. Gerson, C. Pütz, E. Vogel, J. Chem. Soc. Perkin Trans. 2, 1996, 541.
6. E. Vogel, W. Haas, B. Knipp. J. Lex, H. Schmickler, Angew. Chem. 1988, 100, 445; Angew: Chem. Int. Ed. Engl. 1988, 27, 406; W. Haas, B. Knipp, M. Sicken, J. Lex, E. Vogel, ibid. 1988, 100, 448 and 1988, 27, 409; for expanded tetraoxaporphyrin dicalions see: G. Märkl, H. Sauer, P. Kreitmeier, T. Burgemeister, F. Kastner, G. Adolin, H. Nöth, K. Polborn, ibid. 1994, 106, 1211 and 1994, 33, 1151; R. Bachmann, F. Gerson, C. Pütz, E. Vogel, J. Chem. Soc. Perkin Trans. 2, 1996, 541.
7. E. Vogel, W. Haas, B. Knipp. J. Lex, H. Schmickler, Angew. Chem. 1988, 100, 445; Angew: Chem. Int. Ed. Engl. 1988, 27, 406; W. Haas, B. Knipp, M. Sicken, J. Lex, E. Vogel, ibid. 1988, 100, 448 and 1988, 27, 409; for expanded tetraoxaporphyrin dicalions see: G. Märkl, H. Sauer, P. Kreitmeier, T. Burgemeister, F. Kastner, G. Adolin, H. Nöth, K. Polborn, ibid. 1994, 106, 1211 and 1994, 33, 1151; R. Bachmann, F. Gerson, C. Pütz, E. Vogel, J. Chem. Soc. Perkin Trans. 2, 1996, 541.
8. a) For mono- and dioxaporphyrins see: A. W. Johnson in Porphyrins and Metalloporphyrins (Ed.: K. M. Smith), Elsevier, Amsterdam, 1975, p. 729;
9. b) L. Latos-Grazyński, E. Pacholska, P. J. Chmielewski, M. M. Olmstcad, A. L. Balch, Angew: Chem. 1995, 107, 2467; Angew. Chem. Inl. Ed. Engl. 1995, 34, 2252;
10. b) L. Latos-Grazyński, E. Pacholska, P. J. Chmielewski, M. M. Olmstcad, A. L. Balch, Angew: Chem. 1995, 107, 2467; Angew. Chem. Inl. Ed. Engl. 1995, 34, 2252;
11. c) dioxa-5-oxophlorins are described by T. D. Lash, Y. L. S.-T. Armiger, J. Heterocycl. Chem. 1991, 28, 965; T. D. Lash, J. Org. Chem. 1992, 57, 4312.
12. c) dioxa-5-oxophlorins are described by T. D. Lash, Y. L. S.-T. Armiger, J. Heterocycl. Chem. 1991, 28, 965; T. D. Lash, J. Org. Chem. 1992, 57, 4312.
13. 2 complexes, respectively, with nickel chloride (the latter with pseudooctahedral coordination geometry): P. J. Chmielewski, L. Latos-Grażyński, M. M. Olmstead, A. L. Balch, Chem. Eur. J. 1997, 3, 268; Z. Gross, Technion, Haifa (Israel), personal communication.
14. 2 complexes, respectively, with nickel chloride (the latter with pseudooctahedral coordination geometry): P. J. Chmielewski, L. Latos-Grażyński, M. M. Olmstead, A. L. Balch, Chem. Eur. J. 1997, 3, 268; Z. Gross, Technion, Haifa (Israel), personal communication.
15. [4| R. Bachmann, F. Gerson, G. Gescheidt, E. Vogel, J. Am. Chem. Soc. 1992, 114, 10855; E. Vogel, Pure Appl. Chem. 1993, 65, 143.
16. [4| R. Bachmann, F. Gerson, G. Gescheidt, E. Vogel, J. Am. Chem. Soc. 1992, 114, 10855; E. Vogel, Pure Appl. Chem. 1993, 65, 143.
17. E. Vogel, P. Röhrig, M. Sicken, B. Knipp, A. Herrmann, M. Pohl, H. Schmickler, J. Lex, Angew. Chem. 1989, 101, 1683; Angew. Chem. Int. Ed. Engl. 1989, 28, 1651.
18. E. Vogel, P. Röhrig, M. Sicken, B. Knipp, A. Herrmann, M. Pohl, H. Schmickler, J. Lex, Angew. Chem. 1989, 101, 1683; Angew. Chem. Int. Ed. Engl. 1989, 28, 1651.
19. There are a number of reports on mono- and dithiaporphyrins as well as diselenaporphyrins: a) M. J. Broadhurst, R. Grigg, A. W. Johnson, J. Chem. Soc. C 1971, 3681; b) A. Ulman, J. Manassen, J. Am. Chem. Soc. 1975, 97, 6540; c) A. Ulman, J. Manassen, F. Frolow, D. Rabinovich, ibid. 1979, 101, 7055; d) R. L. Hill, M. Gouterman, A. Ulman, Inorg. Chem. 1982, 21, 1450.
20. There are a number of reports on mono- and dithiaporphyrins as well as diselenaporphyrins: a) M. J. Broadhurst, R. Grigg, A. W. Johnson, J. Chem. Soc. C 1971, 3681; b) A. Ulman, J. Manassen, J. Am. Chem. Soc. 1975, 97, 6540; c) A. Ulman, J. Manassen, F. Frolow, D. Rabinovich, ibid. 1979, 101, 7055; d) R. L. Hill, M. Gouterman, A. Ulman, Inorg. Chem. 1982, 21, 1450.
21. There are a number of reports on mono- and dithiaporphyrins as well as diselenaporphyrins: a) M. J. Broadhurst, R. Grigg, A. W. Johnson, J. Chem. Soc. C 1971, 3681; b) A. Ulman, J. Manassen, J. Am. Chem. Soc. 1975, 97, 6540; c) A. Ulman, J. Manassen, F. Frolow, D. Rabinovich, ibid. 1979, 101, 7055; d) R. L. Hill, M. Gouterman, A. Ulman, Inorg. Chem. 1982, 21, 1450.
22. There are a number of reports on mono- and dithiaporphyrins as well as diselenaporphyrins: a) M. J. Broadhurst, R. Grigg, A. W. Johnson, J. Chem. Soc. C 1971, 3681; b) A. Ulman, J. Manassen, J. Am. Chem. Soc. 1975, 97, 6540; c) A. Ulman, J. Manassen, F. Frolow, D. Rabinovich, ibid. 1979, 101, 7055; d) R. L. Hill, M. Gouterman, A. Ulman, Inorg. Chem. 1982, 21, 1450.
23. For the coordination chemistry of monothia- and monoselenaporphyrins see: e) L. Latos-Grażyński, J. Lisowski, M. M. Olmstead, A. L. Batch, J. Am. Chem. Soc. 1987, 109, 4428; f) Inorg. Chem. 1989, 28, 1183; g) R. P. Pandian, T. K. Chandrashekar, J. Chem. Soc. Dalton Trans. 1993, 119; h) M. Ravikanth, T. K. Chandrashekar, Struct. Bonding (Berlin) 1995, 82, 105; i) L. Latos-Grażyński, E. Pacholska, P. J. Chmielewski, M. M. Olmstead, A. L. Balch, Inorg. Chem. 1996, 35, 566; j) a monoselenasapphyrin was reported by J. Lisowski, J. L. Sessler, V. Lynch, Inorg. Chem. 1995, 34, 3567.
24. For the coordination chemistry of monothia- and monoselenaporphyrins see: e) L. Latos-Grażyński, J. Lisowski, M. M. Olmstead, A. L. Batch, J. Am. Chem. Soc. 1987, 109, 4428; f) Inorg. Chem. 1989, 28, 1183; g) R. P. Pandian, T. K. Chandrashekar, J. Chem. Soc. Dalton Trans. 1993, 119; h) M. Ravikanth, T. K. Chandrashekar, Struct. Bonding (Berlin) 1995, 82, 105; i) L. Latos-Grażyński, E. Pacholska, P. J. Chmielewski, M. M. Olmstead, A. L. Balch, Inorg. Chem. 1996, 35, 566; j) a monoselenasapphyrin was reported by J. Lisowski, J. L. Sessler, V. Lynch, Inorg. Chem. 1995, 34, 3567.
25. For the coordination chemistry of monothia- and monoselenaporphyrins see: e) L. Latos-Grażyński, J. Lisowski, M. M. Olmstead, A. L. Batch, J. Am. Chem. Soc. 1987, 109, 4428; f) Inorg. Chem. 1989, 28, 1183; g) R. P. Pandian, T. K. Chandrashekar, J. Chem. Soc. Dalton Trans. 1993, 119; h) M. Ravikanth, T. K. Chandrashekar, Struct. Bonding (Berlin) 1995, 82, 105; i) L. Latos-Grażyński, E. Pacholska, P. J. Chmielewski, M. M. Olmstead, A. L. Balch, Inorg. Chem. 1996, 35, 566; j) a monoselenasapphyrin was reported by J. Lisowski, J. L. Sessler, V. Lynch, Inorg. Chem. 1995, 34, 3567.
26. For the coordination chemistry of monothia- and monoselenaporphyrins see: e) L. Latos-Grażyński, J. Lisowski, M. M. Olmstead, A. L. Batch, J. Am. Chem. Soc. 1987, 109, 4428; f) Inorg. Chem. 1989, 28, 1183; g) R. P. Pandian, T. K. Chandrashekar, J. Chem. Soc. Dalton Trans. 1993, 119; h) M. Ravikanth, T. K. Chandrashekar, Struct. Bonding (Berlin) 1995, 82, 105; i) L. Latos-Grażyński, E. Pacholska, P. J. Chmielewski, M. M. Olmstead, A. L. Balch, Inorg. Chem. 1996, 35, 566; j) a monoselenasapphyrin was reported by J. Lisowski, J. L. Sessler, V. Lynch, Inorg. Chem. 1995, 34, 3567.
27. For the coordination chemistry of monothia- and monoselenaporphyrins see: e) L. Latos-Grażyński, J. Lisowski, M. M. Olmstead, A. L. Batch, J. Am. Chem. Soc. 1987, 109, 4428; f) Inorg. Chem. 1989, 28, 1183; g) R. P. Pandian, T. K. Chandrashekar, J. Chem. Soc. Dalton Trans. 1993, 119; h) M. Ravikanth, T. K. Chandrashekar, Struct. Bonding (Berlin) 1995, 82, 105; i) L. Latos-Grażyński, E. Pacholska, P. J. Chmielewski, M. M. Olmstead, A. L. Balch, Inorg. Chem. 1996, 35, 566; j) a monoselenasapphyrin was reported by J. Lisowski, J. L. Sessler, V. Lynch, Inorg. Chem. 1995, 34, 3567.
28. For the coordination chemistry of monothia- and monoselenaporphyrins see: e) L. Latos-Grażyński, J. Lisowski, M. M. Olmstead, A. L. Batch, J. Am. Chem. Soc. 1987, 109, 4428; f) Inorg. Chem. 1989, 28, 1183; g) R. P. Pandian, T. K. Chandrashekar, J. Chem. Soc. Dalton Trans. 1993, 119; h) M. Ravikanth, T. K. Chandrashekar, Struct. Bonding (Berlin) 1995, 82, 105; i) L. Latos-Grażyński, E. Pacholska, P. J. Chmielewski, M. M. Olmstead, A. L. Balch, Inorg. Chem. 1996, 35, 566; j) a monoselenasapphyrin was reported by J. Lisowski, J. L. Sessler, V. Lynch, Inorg. Chem. 1995, 34, 3567.
29. E. Vogel, J. Dörr, A. Herrmann, J. Lex, H. Schmickler, P. Walgenbach, J. P. Gisselbrecht, M. Gross, Angew. Chem. 1993, 105, 1667; Angew. Chem. Int. Ed. Engl. 1993, 32, 1597.
30. E. Vogel, J. Dörr, A. Herrmann, J. Lex, H. Schmickler, P. Walgenbach, J. P. Gisselbrecht, M. Gross, Angew. Chem. 1993, 105, 1667; Angew. Chem. Int. Ed. Engl. 1993, 32, 1597.
31. E. Vogel, M. Pohl, A. Herrmann, T. Wiß, C. König, J. Lex, M. Gross, J. P. Gisselbrecht, Angew: Chem. 1996, 108, 1677; Angew. Chem. Int. Ed. Engl. 1996, 35, 1520.
32. E. Vogel, M. Pohl, A. Herrmann, T. Wiß, C. König, J. Lex, M. Gross, J. P. Gisselbrecht, Angew: Chem. 1996, 108, 1677; Angew. Chem. Int. Ed. Engl. 1996, 35, 1520.
33. [5] Despite the advances in the chemistry of tellurium (see N. Petragnani, Tellurium in Organic Syntheses, Academic Press, London, 1994), the synthetic route to the tellurium analogue of 4, 5, and 6 still appears to be strewn with difficulties.
34. 2Se and methyl chloroacetate see: H. Rheinboldt in Methoden Org. Chem. (Houben-Weyl), 4th. ed. vol 9, p. 976:
35. 4 in THF, 1 h, 25°C; 7 precipitated from n-hexane as a colorless, mother-of-pearl-like solid, m.p. 21°C (yield 94%).
36. The compounds 8 and 9 were identified on the basis of their characteristic violet color, which appeared on the thin layer chromatograms [n-hexane/ toluene (4/1)] after treatment with nitric acid vapor (the color of the first fraction disappeared after a short time).
37. Calculated from the relevant bond angles for thiophene and selenophene given in C. W. Bird, G. W. H. Cheeseman in Comprehensive Heterocyclic Chemistry, Vol. 4, Part 3 (Eds.: A. R. Katritzky, C. W. Rees), Pergamon, Oxford, 1984, p. 3.
38. B. Franck, A. Nonn, K. Fuchs, M. Gosmann, Liebigs Ann. Chem. 1994, 503; G. Bringmann, B. Franck, ibid. 1982, 1272; see also L. F. Tietze, H. Geissler, Angew. Chem. 1993, 105, 1087; Angew. Chem. Int. Ed. Engl. 1993, 32, 1038.
39. B. Franck, A. Nonn, K. Fuchs, M. Gosmann, Liebigs Ann. Chem. 1994, 503; G. Bringmann, B. Franck, ibid. 1982, 1272; see also L. F. Tietze, H. Geissler, Angew. Chem. 1993, 105, 1087; Angew. Chem. Int. Ed. Engl. 1993, 32, 1038.
40. B. Franck, A. Nonn, K. Fuchs, M. Gosmann, Liebigs Ann. Chem. 1994, 503; G. Bringmann, B. Franck, ibid. 1982, 1272; see also L. F. Tietze, H. Geissler, Angew. Chem. 1993, 105, 1087; Angew. Chem. Int. Ed. Engl. 1993, 32, 1038.
41. B. Franck, A. Nonn, K. Fuchs, M. Gosmann, Liebigs Ann. Chem. 1994, 503; G. Bringmann, B. Franck, ibid. 1982, 1272; see also L. F. Tietze, H. Geissler, Angew. Chem. 1993, 105, 1087; Angew. Chem. Int. Ed. Engl. 1993, 32, 1038.
42. 1/2. Programs used: MolEN (Enraf-Nonius) for structure determination and SHELXL-93 (G. M. Sheldrick, University of Göttingen) for refinement. Calculations were carried out at the Regionales Rechenzentrum der Universität Köln. The crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-100-118. Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road, Cambridge, CB21EZ, UK (fax: Int code +(1223)336-033; e-mail: deposit@chemcrys.cam.ac.uk).
43. Cyclovoltammetric studies on 6 indicate two reduction waves, which in terms of the electron transitions cannot be interpreted unambiguously because of the strong broadening.
44. The reduction took place under an inert atmosphere in a reaction flask that was connected through a frit to a NMR tube.
45. H. Spiesecke, W. G. Schneider, Tetrahedron Lett. 1961, 468; B. Eliasson, U. Edlund, K. Müllen, J. Chem. Soc. Perkin Trans. 2 1986, 937; G. A. Olah, G. D. Mateescu, J. Am. Chem. Soc. 1970, 92, 1430.
46. H. Spiesecke, W. G. Schneider, Tetrahedron Lett. 1961, 468; B. Eliasson, U. Edlund, K. Müllen, J. Chem. Soc. Perkin Trans. 2 1986, 937; G. A. Olah, G. D. Mateescu, J. Am. Chem. Soc. 1970, 92, 1430.
47. H. Spiesecke, W. G. Schneider, Tetrahedron Lett. 1961, 468; B. Eliasson, U. Edlund, K. Müllen, J. Chem. Soc. Perkin Trans. 2 1986, 937; G. A. Olah, G. D. Mateescu, J. Am. Chem. Soc. 1970, 92, 1430.
48. The fairly good correlation of experimental and calculated Δδ values is astonishing, because the possibility that the heteroatoms in both 6 and 11 could carry charge was not taken into consideration.