Comparative Thermochemistry of Metalloporphyrin Isomers as a Function of Metal Ion Size. A Possible Insight into Nature's Choice of Porphyrin over Isomeric Ligands

Inorganic Chemistry

Volumn 37, Issue 24, 1998, Pages 6276-6280

  Ghosh, Abhik ^a   Vangberg, Torgil ^a  

^a UNIVERSITY OF TROMSØ   (Norway)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000633839     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic9807994     Document Type: Article

References (22)

1. (a) Vogel, E. J. Heterocycl. Chem. 1996, 33, 1461.
2. (b) Sessler, J. L.; Weghorn, S. J. Expanded, Contracted and Isomeric Porphyrins; Elsevier: Amsterdarn, 1997.
3. (a) Porphycene: Vogel, E.; Köcher, M.; Schmickler, H.; Lex, J. Angew. Chem., Int. Ed. Engl. 1986, 25, 257.
4. (b) (i) Corrphycene: Sessler, J. L.; Brucker, E. A.; Weghorn, S. J.; Kisters, M.; Schäfer, M.; Lex, J.; Vogel, E. Angew. Chem., Int. Ed. Engl. 1994, 33, 2308. Aukaloo, M, A.; Guilard, R. New J. Chem. 1994, 18, 1205. Falk, H.; Chen, Q.-Q. Monatsh. Chem. 1996, 127, 69.
5. (b) (i) Corrphycene: Sessler, J. L.; Brucker, E. A.; Weghorn, S. J.; Kisters, M.; Schäfer, M.; Lex, J.; Vogel, E. Angew. Chem., Int. Ed. Engl. 1994, 33, 2308. Aukaloo, M, A.; Guilard, R. New J. Chem. 1994, 18, 1205. Falk, H.; Chen, Q.-Q. Monatsh. Chem. 1996, 127, 69.
6. (b) (i) Corrphycene: Sessler, J. L.; Brucker, E. A.; Weghorn, S. J.; Kisters, M.; Schäfer, M.; Lex, J.; Vogel, E. Angew. Chem., Int. Ed. Engl. 1994, 33, 2308. Aukaloo, M, A.; Guilard, R. New J. Chem. 1994, 18, 1205. Falk, H.; Chen, Q.-Q. Monatsh. Chem. 1996, 127, 69.
7. (c)Hemiporphycene: Callot, H. J.; Rohrer, A.; Tschamber, T.; Metz, B. New J. Chem. 1995, 19, 155.
8. (d)Isoporphycene: Vogel, E.; Broring, M.; Erben, C.; Demuth, R. Angew. Chem., Int. Ed. Engl. 1997, 36, 353.
9. For a review on carbaporphyrins, see: Nilsen, H. J.; Ghosh, A. Acta Chem. Scand. 1998, 52, 827.
10. (a) Chmielewski, P. J.; Latos-Grazynski, L.; Glowiak, T. J. Am. Chem. Soc. 1996, 118, 5690 and references therein.
11. (b) For a theoretical study, see: Ghosh, A. Angew. Chem., Int. Ed. Engl. 1995, 34, 1028.
12. Ghosh, A.; Jynge, K. J. Phys. Chem. B 1997, 101, 5459.
13. Wu, Y.-D.; Chan, K. W. K.; Yip, C.-P.; Vogel, E.; Plattner, D. A.; Houk, K. N. J. Org. Chem. 1997, 62, 9240.
14. Ghosh, A.; Jynge, K. Chem. Eur. J. 1997, 3, 823.
15. All calculations were carried out with the ADF program system, using the VWN local exchange-correlation functional (Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 55, 1200), the Perdew - Wang 1991 nonlocal corrections (Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Phys. Rev. B 1992, 46, 6671), triple-ζ plus polarization Slater-type basis sets, a fine mesh for numerical integration of matrix elements, a spin-restricted formalism, and full geometry optimizations within the symmetry constraints shown in Table 2. For additional technical details, the reader is referred to the ADF program manual which can be obtained from Scientific Computing and Modelling, Department of Theoretical Chemistry, Vrije Universiteit, 1081 HV Amsterdam, The Netherlands. Except for the trans-[3.0.1.0.] dianion and complexes, all molecules were required to be planar as a result of the symmetry constraints. The mirror plane in the trans-[3.0.1.0.] systems is perpendicular to the mean molecular plane and thus permits nonplanarity.
16. All calculations were carried out with the ADF program system, using the VWN local exchange-correlation functional (Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 55, 1200), the Perdew - Wang 1991 nonlocal corrections (Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Phys. Rev. B 1992, 46, 6671), triple-ζ plus polarization Slater-type basis sets, a fine mesh for numerical integration of matrix elements, a spin-restricted formalism, and full geometry optimizations within the symmetry constraints shown in Table 2. For additional technical details, the reader is referred to the ADF program manual which can be obtained from Scientific Computing and Modelling, Department of Theoretical Chemistry, Vrije Universiteit, 1081 HV Amsterdam, The Netherlands. Except for the trans-[3.0.1.0.] dianion and complexes, all molecules were required to be planar as a result of the symmetry constraints. The mirror plane in the trans-[3.0.1.0.] systems is perpendicular to the mean molecular plane and thus permits nonplanarity.
17. For a review of the performance of density functional calculations on porphyrins, see: Ghosh, A. Acc. Chem. Res. 1998, 31, 189.
18. Zandler, M. E.; D'Souza, F. D. J. Mol. Struct. (THEOCHEM) 1997, 401, 301.
19. 10 shown in Table 2 are in excellent agreement with DFT results, but certain others are not and the magnesium results in ref 10 certainly seem to be very unreasonable.
20. (a) Shannon, R. D.; Prewitt, C. T. Acta Crystallogr. B 1969, 25, 925.
21. (b) Shanon, R. D. Acta Crystallogr. A 1976, 32, 751.
22. These numbers suggest that the errors in energy due to the use of the symmetry constraints shown in Table 2 should be quite modest and, presumably, on the order of a couple of kcal/mol.