메뉴 건너뛰기




Volumn 130, Issue 14, 2008, Pages 4628-4636

Spectroscopic and electronic structure studies of symmetrized models for reduced members of the dimethylsulfoxide reductase enzyme family

Author keywords

[No Author keywords available]

Indexed keywords

ABSORPTION; ELECTRONIC STRUCTURE; EXCITED STATES; LIGANDS; MATHEMATICAL MODELS; SPECTROSCOPIC ANALYSIS;

EID: 41849127092     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja074691b     Document Type: Article
Times cited : (32)

References (55)
  • 1
  • 2
    • 0003301298 scopus 로고
    • Stiefel, E. I, Coucouvanis, D, Newton, W. E, Eds, American Chemical Society
    • Stiefel, E. I. Molybdenum Enzymes, Cofactors, and Model Systems; Stiefel, E. I., Coucouvanis, D., Newton, W. E., Eds.; American Chemical Society: 1993; pp 1-21.
    • (1993) Molybdenum Enzymes, Cofactors, and Model Systems , pp. 1-21
    • Stiefel, E.I.1
  • 32
    • 41849128679 scopus 로고    scopus 로고
    • Gaussian 98, Revision A.7, Gaussian, Inc., Pittsburgh, PA, 1998.
    • Gaussian 98, Revision A.7, Gaussian, Inc., Pittsburgh, PA, 1998.
  • 45
    • 41849096875 scopus 로고    scopus 로고
    • In keeping with literature precedence for pyranopterin molybdenum enzyme active sites and models, we chose to label the lowest energy Mo orbital as dxy and the most destabilized Mo orbital as d x2-y2. Thus, in C2ν symmetry the dxy orbital transforms as a1 and the dx2- y2 orbital transforms as a2
    • 2.
  • 46
    • 41849098717 scopus 로고    scopus 로고
    • The position of the apical ligand methyl group, varied from bisecting a single dithiolene ligand (in the xz plane) to bisecting the two dithiolene ligands (in the yz plane), does not affect the general bonding scheme and only causes slight shifts of the molecular orbital energies, likely as a result of differential mixing of dithiolene S and apical chalcogen orbitals.
    • The position of the apical ligand methyl group, varied from bisecting a single dithiolene ligand (in the xz plane) to bisecting the two dithiolene ligands (in the yz plane), does not affect the general bonding scheme and only causes slight shifts of the molecular orbital energies, likely as a result of differential mixing of dithiolene S and apical chalcogen orbitals.
  • 48
    • 41849086104 scopus 로고    scopus 로고
    • Scaling factor of 0.9613 used per ref 34
    • Scaling factor of 0.9613 used per ref 34.
  • 50
    • 41849091298 scopus 로고    scopus 로고
    • The OPT2 geometry is nearly identical to the crystal structure geometry, except mat the C-O-Mo angle is much more obtuse in the crystal structure at 162°, whereas the angle optimizes to ∼135° in all of the calculations. The effect of constraining this angle in addition to the two dihedrals constrained previously was also tested and resulted in a marginal further destabilization of 0.002 eV with the HOMO essentially unchanged in character and orientation from Figure 6f.
    • The OPT2 geometry is nearly identical to the crystal structure geometry, except mat the C-O-Mo angle is much more obtuse in the crystal structure at 162°, whereas the angle optimizes to ∼135° in all of the calculations. The effect of constraining this angle in addition to the two dihedrals constrained previously was also tested and resulted in a marginal further destabilization of 0.002 eV with the HOMO essentially unchanged in character and orientation from Figure 6f.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.