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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
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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.
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Scaling factor of 0.9613 used per ref 34
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Scaling factor of 0.9613 used per ref 34.
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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.
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