Direct incorporation of a ferric ion in the porphyrinogen core: Tetrakis(cyclohexyl)iron porphyrinogen anion with different conformers and its reaction with iodine

Inorganic Chemistry

Volumn 44, Issue 22, 2005, Pages 7699-7701

  Bhattacharya, Dibyendu ^a   Dey, Soumen ^a   Maji, Suman ^a   Pal, Kuntal ^a   Sarkar, Sabyasachi ^a  

^a INDIAN INSTITUTE OF TECHNOLOGY KANPUR   (India)

Author keywords

[No Author keywords available]

Indexed keywords

ANION; IODINE; IRON; LIGAND; PORPHYRIN; PORPHYRINOGEN; TETRAKIS(CYCLOHEXYL)IRON PORPHYRINOGEN;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; METABOLISM; OXIDATION REDUCTION REACTION;

ANIONS; IODINE; IRON; LIGANDS; MOLECULAR STRUCTURE; OXIDATION-REDUCTION; PORPHYRINOGENS; PORPHYRINS;

EID: 27744572917     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic050890p     Document Type: Article

References (17)

1. (a) Elder, G. H. In Iron in biochemistry and medicine II; Jacobs, A., Worwood, M., Eds.; Academic Press: London, 1980; pp 245-292.
2. (b) Huszánk, R.; Horváth, O. Chem. Commun. 2005, 2, 224-226.
3. (a) Floriani, C.; Floriani-Moro, R. In The Porphyrin Handbook; Kadsish, K. M., Smith, K. M., Guilard, R., Eds.; Academic Press: New York, 2000; Vol. 3, p 389.
4. (b) A hexacoordinated V complex using V(III) as the starting material has been reported. See: Jubb, J.; Gambarotta, S. J. Am. Chem. Soc. 1993, 115, 10410-10411.
5. (a) Judd, J.; Jacoby, D.; Floriani, C.; Chiesi-Villa, A.; Rizzoli, C. Inorg. Chem. 1992, 31, 1306.
6. (b) A very similar stoichiometric reaction yielded the corresponding Ru(II) complex. See: Bonomo, L.; Stern, C.; Solari, E.; Scopelliti, R.; Floriani, C. Angew. Chem., Int. Ed. 2001, 40 (8), 1449-1452.
7. Jacoby, D.; Floriani, C.; Chiesi-Villa, A.; Rizzoli, C. J. Chem. Soc., Chem. Commun. 1991, 220.
8. Bachmann, J.; Nocera, D. G. J. Am. Chem. Soc. 2005, 127, 4730-4743.
9. Detail syntheses of 1-3 are in the Supporting Information.
10. int = 0.017); GOF = 1.067, final R1 = 0.0746 [I > 2σ(I)], wR2 = 0.2199.
11. Evans, D. F. J. Chem. Soc. 1959, 2003.
12. B.
13. Calculations were carried out with the CAChe 5.03 program of Fujitsu Ltd., using a ZINDO semiempirical method.
14. Angelis, S. D.; Solari, E.; Floriani, C.; Chiesi-Villa, A.; Rizzoli, C. J. Am. Chem. Soc. 1994, 116, 5691-5701.
15. - ion pair in the crystal.
16. Pople, J. A.; et al. Gaussian 03, revision B.04; Gaussian, Inc.: Pittsburgh, PA, 2003 (see the Supporting Information).
17. DFT calculations have been carried out by employing a B3LYP hybrid functional using the Gaussian 03 program; molecular orbitals were visualized using G View. The 6-31 g** basis set was used for the C, N, and H atoms, and MidiX was used for the I atom; the effective core potential basis set LANL2DZ was used for the Fe atom. The geometry was taken from the crystal structure. Because spin restriction is lifted, there is no common spatial wave function for each α and β spin pair, and two manifolds of "orbitals" are drawn separately. For three conformers (parts a-c in Figure 2) and for 3 (Figure 3), the β spinator bears 90% d character.