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Volumn 127, Issue 6, 2005, Pages 1675-1689

Synthesis, structure determination, and spectroscopic/computational characterization of a series of Fe(II)-thiolate model complexes: Implications for Fe-S bonding in superoxide reductases

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BONDS; ELECTROCHEMISTRY; ELECTRONIC STRUCTURE; PROBABILITY DENSITY FUNCTION; SYNTHESIS (CHEMICAL); X RAY CRYSTALLOGRAPHY;

EID: 13644271306     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja046939s     Document Type: Article
Times cited : (47)

References (78)
  • 25
    • 0005867084 scopus 로고    scopus 로고
    • Molecular Structure Corporation, Inc.: The Woodlands, TX
    • (a) TeXsan for Windows V 1.02; Molecular Structure Corporation, Inc.: The Woodlands, TX.
    • TeXsan for Windows V 1.02
  • 30
    • 13644268874 scopus 로고    scopus 로고
    • note
    • In all cases, the g-values were in the range 2.01-2.08, and variations in these values had only negligible effects on the quality of the resulting fits. Specifically, our analysis revealed that the overall shapes of the VTVH-MCD magnetization curves are determined principally by the ZFS parameters, not the g-values.
  • 40
    • 13644257184 scopus 로고    scopus 로고
    • Unpublished results
    • Ahlrichs, R. Unpublished results.
    • Ahlrichs, R.1
  • 50
    • 13644253336 scopus 로고    scopus 로고
    • note
    • 4cyclam over the pyridyl-pendant diazacyclooctane ligand.
  • 51
    • 13644266414 scopus 로고    scopus 로고
    • note
    • The geometric parameter τ is defined as τ = |(β - α)|/60, where α and β are the two trans basal angles in psuedo-square pyramidal geometry (see ref 41). In idealized square-planar geometries, α = β, but trigonal distortions result in α ≠ β.
  • 55
    • 13644256360 scopus 로고    scopus 로고
    • note
    • -1 (data not shown).
  • 58
    • 13644251070 scopus 로고    scopus 로고
    • note
    • Although the solid-state sample of 2 contains two crystallographically distinct complexes (cations I and II), the structural differences are too small to cause the appearance of two sets of bands that can be resolved in the MCD spectrum but may possibly lead to a general broadening of the bands.
  • 60
    • 13644270867 scopus 로고    scopus 로고
    • note
    • -1. However, in all instances, the ZFS parameters that provided the best fits of the low-energy VTVH-MCD data sets also provided excellent fits of the corresponding high-energy data sets.
  • 63
    • 13644250228 scopus 로고    scopus 로고
    • note
    • For these S = 2 complexes, spin polarization lowers the energies of the majority-spin (i.e., spin-up) Fe d orbitals relative to their minority-spin (i.e., spin-down) counterparts, resulting in substantial mixing of the former with ligand-based orbitals. The natures of the Fe-ligand bonding interactions are therefore inferred from the ligand- and Fe d-based spin-down MOs that are considerably less mixed than their spin-up counterparts.
  • 64
    • 13644261710 scopus 로고    scopus 로고
    • note
    • 2-based orbitals.
  • 65
    • 13644270866 scopus 로고    scopus 로고
    • note
    • x2-y2 orbitals.
  • 66
    • 13644269913 scopus 로고    scopus 로고
    • note
    • 2 π*-acceptor orbitals.
  • 67
    • 13644258006 scopus 로고    scopus 로고
    • note
    • For complex 2, the angles reported in the text are averaged over both crystallographically independent cations.
  • 68
    • 13644255574 scopus 로고    scopus 로고
    • note
    • Note that for both complexes deviations of these angles from 90° give rise to somewhat mixed σ- and π-bonding interactions.
  • 70
    • 13644258615 scopus 로고    scopus 로고
    • note
    • -1 to facilitate comparison with the experimental spectrum.
  • 71
    • 13644266415 scopus 로고    scopus 로고
    • note
    • It is important to note that bands that are intense in the absorption spectrum are often weak in the MCD spectrum, and it is therefore not surprising that the relative intensities of bands 6 and 7 are dramatically different in the two spectra.
  • 72
    • 13644268876 scopus 로고    scopus 로고
    • note
    • -1 (Figure 4).
  • 73
    • 13644267238 scopus 로고    scopus 로고
    • note
    • -1. It is therefore apparent that, although DFT provides a qualitatively correct Fe d-orbital splitting pattern for 3, the experimental Fe d-orbital splitting pattern is, in fact, reminiscent of an "effective" electronic symmetry intermediate between trigonal bipyramidal and square pyramidal.
  • 76
    • 13644249404 scopus 로고    scopus 로고
    • note
    • red (see ref 4).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.