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Volumn 45, Issue 7, 2006, Pages 2795-2811

Spectroscopic properties and electronic structure of five- and six-coordinate iron(II) porphyrin NO complexes: Effect of the axial N-donor ligand

Author keywords

[No Author keywords available]

Indexed keywords

FERROUS ION; LIGAND; NITRIC OXIDE; PORPHYRIN;

EID: 33645870443     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic050865j     Document Type: Article
Times cited : (156)

References (107)
  • 40
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    • Solomon, E. I., Lever, A. B. P., Eds.; Wiley: New York
    • Westcott, B. L.; Enemark, J. H. Transition Metal Nitrosyls; Solomon, E. I., Lever, A. B. P., Eds.; Wiley: New York, 1999; Vol. 2, pp 403-450.
    • (1999) Transition Metal Nitrosyls , vol.2 , pp. 403-450
    • Westcott, B.L.1    Enemark, J.H.2
  • 56
    • 33645859157 scopus 로고    scopus 로고
    • note
    • IINO complexes in this study, complexes 2 and 2-F were prepared by very slow crystallization and obtained as pure materials. However, the isolation of the pure 6C complex using TMP as the ligand was unsuccessful and always yielded mixtures of 1-Me and [Fe(TMP)(MI)(NO)] as evidenced by IR spectroscopy.
  • 62
    • 16244422272 scopus 로고    scopus 로고
    • Max-Planck Institut für Bioanorganische Chemie: Mülheim/Ruhr, Germany
    • Neese, F. ORCA, version 2.2; Max-Planck Institut für Bioanorganische Chemie: Mülheim/Ruhr, Germany, 2004.
    • (2004) ORCA, Version 2.2
    • Neese, F.1
  • 67
    • 33645869966 scopus 로고    scopus 로고
    • note
    • o).
  • 70
    • 33645877207 scopus 로고    scopus 로고
    • note
    • In this respect, it is interesting to note that NO behaves like a normal N-donor ligand in these ligand-binding experiments.
  • 80
    • 33645884218 scopus 로고    scopus 로고
    • note
    • xy undergoes a σ bond with the porphyrin and can therefore be classified as an "e" orbital.
  • 81
    • 33645849948 scopus 로고    scopus 로고
    • note
    • 2u〈81〉.
  • 82
    • 33645870513 scopus 로고    scopus 로고
    • note
    • yz (β〈126〉) for 2. This leads to the transfer of a small additional amount of spin density from NO to iron in 1 relative to 2.
  • 84
    • 33645893329 scopus 로고    scopus 로고
    • note
    • 2] (cf. Figure 2), these signals are observed at 8.97 ppm, which is close to the value of ∼8.1 ppm for 2. In contrast, these hydrogens show a stronger paramagnetic shift to 5.95 ppm in 1. Correspondingly, the calculated spin densities on the pyrrole hydrogens are 2-4 times larger in 1 than they are in 2.
  • 87
    • 0002312013 scopus 로고
    • Optical Spectra and Electronic Structure of Porphyrins and Related Rings
    • Dolphin, D., Ed.; Academic Press: New York
    • Gouterman, M. Optical Spectra and Electronic Structure of Porphyrins and Related Rings. In The Porphyrins; Dolphin, D., Ed.; Academic Press: New York, 1978; Vol. III.
    • (1978) The Porphyrins , vol.3
    • Gouterman, M.1
  • 89
    • 33645841444 scopus 로고
    • Lever, A. B. P., Gray, H. B., Eds.; Addison-Wesley: Reading, MA
    • (b) Spiro, T. G. In Iron Porphyrins; Lever, A. B. P., Gray, H. B., Eds.; Addison-Wesley: Reading, MA, 1983; Part 2.
    • (1983) Iron Porphyrins , Issue.2 PART
    • Spiro, T.G.1
  • 92
    • 33645893875 scopus 로고    scopus 로고
    • note
    • Because of a disorder in the crystal, the experimental structure of 1 in ref 27 has a planar TPP ring. This, however, is certainly not the case in the actual complex and, correspondingly, the INDO/S-CI calculations on this structure lead to a wrong ground state. Therefore, the conformation of the TPP ring from the crystal structure of 2 was applied in the TD-DFT calculation for 1. This contributes to the incorrect calculation of the Soret shift.
  • 93
    • 33645872516 scopus 로고    scopus 로고
    • note
    • z2 in 1 (induced by the out-of-plane displacement of iron).
  • 94
    • 33645880886 scopus 로고    scopus 로고
    • note
    • v cannot be calculated with these methods.
  • 96
    • 0015238929 scopus 로고
    • (b) Hoard, J. L. Science 1971, 174, 1295.
    • (1971) Science , vol.174 , pp. 1295
    • Hoard, J.L.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.