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Volumn 129, Issue 34, 2007, Pages 10446-10456

Electronic structure and FeNO conformation of nonheme iron-thiolate-NO complexes: An experimental and DFT study

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL REACTIVITY; COMPLEXATION; CONFORMATIONS; DENSITY FUNCTIONAL THEORY; DISSOCIATION; ELECTRONIC STRUCTURE; LIGANDS; REDOX REACTIONS;

EID: 34548273094     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0719982     Document Type: Article
Times cited : (66)

References (85)
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    • Ignarro, L. J, Ed, Academic Press: San Diego, CA
    • Nitric Oxide: Biology and Pathobiology; Ignarro, L. J., Ed.; Academic Press: San Diego, CA, 2000; pp 3-19.
    • (2000) Nitric Oxide: Biology and Pathobiology , pp. 3-19
  • 24
    • 34548223718 scopus 로고    scopus 로고
    • The superscripts 6 and 7 refer to Enemark-Feltham electron counts, defined as the sum of the numbers of metal d and NO π* electrons: Westcott, B. L.; Enemark, J. H. In Inorganic Electronic Structure and Spectroscopy; Solomon, E. I., Lever, A. B. P., Eds.; Wiley: New York, 1999; 2, pp 403-450.
    • The superscripts 6 and 7 refer to Enemark-Feltham electron counts, defined as the sum of the numbers of metal d and NO π* electrons: Westcott, B. L.; Enemark, J. H. In Inorganic Electronic Structure and Spectroscopy; Solomon, E. I., Lever, A. B. P., Eds.; Wiley: New York, 1999; Vol. 2, pp 403-450.
  • 29
    • 34548209974 scopus 로고    scopus 로고
    • Because of the instability of, n-C5H 11)4N][Fe(NS3)(CO, except under a CO atmosphere, this compound was only incompletely characterized. Some experimental details are as follows. Preparation: 10 mL of an ethanol solution of FeCl2· 4H2O (0.199 g, 1.00 mmol) and, n-C5H 11)4N]Br (3.78 g, 1.00 mmol) were added 5 mL of an ethanol solution of 1.10 mmol of Li3(N(CH2-o-C 6H4S)3, A pale brown precipitate, which formed immediately, redissolved upon the addition of a steady stream of CO to generate a green solution. A crystalline emerald green solid formed and was filtered and dried under a CO atmosphere. Yield: 0.56 g (73 , IR (Nujol, νCO, 1939 cm-1. X-ray analysis: The compound was recrystallized from DMF/EtOH under a CO atmosphere. An emerald-green trigonal prism 0.34 mm x 0.34 mm x 0.14 mm
    • 3, Z = 6). The collected data set was not sufficient for structural analysis.
  • 67
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    • We have also studied the performance of additional functionals, including hybrid functionals, for the various molecules examined. The results do not reveal major differences among the different functionals examined; details of these investigations will be reported in a separate paper in the near future
    • We have also studied the performance of additional functionals, including hybrid functionals, for the various molecules examined. The results do not reveal major differences among the different functionals examined; details of these investigations will be reported in a separate paper in the near future.
  • 68
    • 33746257522 scopus 로고    scopus 로고
    • For a recent discussion of the issue of pure versus hybrid functionals, see
    • For a recent discussion of the issue of pure versus hybrid functionals, see: Ghosh, A. J. Biol. Inorg. Chem. 2006, 11, 671-673.
    • (2006) J. Biol. Inorg. Chem , vol.11 , pp. 671-673
    • Ghosh, A.1
  • 70
    • 34548238222 scopus 로고    scopus 로고
    • In other words, the {FeNO}7 complexes may be best viewed as FeIINO•, which is consistent with recent theoretical analyses of the electron density in related systems.36c,d,j,k,41f Critics of such studies point out that analyses involving partitioning of the electron density among the Fe, N, and O and other atoms are inherently arbitrary and tantamount to characterizing the unknowable (i.e, the oxidation state) in terms of the unobservable atomic charges, Ghosh, A. J. Inorg. Biochem. 2005, 99, vi-viii. On the other hand, like the spin density profiles in this study, X-ray absorption edge energies favor an FeIIINO- description for certain {FeNO}7 systems.41a,b Although attempts to assign metal and NO oxidation states in NO complexes are sometimes thought to generate more heat than light, such a view may be unduly dismissive. The main source of the problem is tha
    • 41a,b Although attempts to assign metal and NO oxidation states in NO complexes are sometimes thought to generate more heat than light, such a view may be unduly dismissive. The main source of the problem is that the concept of oxidation state is not precisely defined. Therefore, controversy can be avoided by carefully defining the criterion or metric used when discussing metal and NO oxidation states.
  • 74
    • 34548249145 scopus 로고    scopus 로고
    • 23 For R = 3,5-dimethylphenyl, cyclopentyl, and isopropyl, the FeNO angles were found to be 160.3(2)°, 172.7(4)°, and 178.2(5)°, respectively. The increasing linearity of the FeNO angles along this series should not be viewed as a failure of our generalizations, but rather as a result of the increasingly sterically hindered nature of the R groups.
    • 23 For R = 3,5-dimethylphenyl, cyclopentyl, and isopropyl, the FeNO angles were found to be 160.3(2)°, 172.7(4)°, and 178.2(5)°, respectively. The increasing linearity of the FeNO angles along this series should not be viewed as a failure of our generalizations, but rather as a result of the increasingly sterically hindered nature of the R groups.
  • 76
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    • Franz, K. J.; Lippard, S. J. J. Am. Chem. Soc. 1999, 121, 10504-10512. Addition/Correction: J. Am. Chem. Soc. 2001, 123, 1266-1266.
    • Franz, K. J.; Lippard, S. J. J. Am. Chem. Soc. 1999, 121, 10504-10512. Addition/Correction: J. Am. Chem. Soc. 2001, 123, 1266-1266.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.