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0013059427
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Bond distances for tetrathiolate are average values for a series of ferrous (CSD: DOKPUO, LAJFUX, PAFVIB, PTHPFE10, VAPVUD, ZAGYIP) and ferric (CSD: BOSTOS, CANCUP, CANDAW, JURHIN, OXYSFEO10) structures.
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0013060401
-
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note
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The negative charge of these complexes in the gas phase contributes to the overestimate of the Fe-X bond distances. The deviation is larger for the tetrachloride, which is unsurprising because of the poorer charge distribution in this complex relative to the tetrathiolate.
-
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-
-
42
-
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0013109182
-
-
note
-
The relationship between the distorting force and the bond changes upon oxidation for the Morse-type potential is compared to that occurring in a harmonic field in the Supporting Information. The linear relationship in a harmonic field is dampened by the anharmonicity in the Morse potential; this deviation increases as the distorting force increases.
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x2-y2 orbital is lowest in energy and becomes the RAMO.
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53
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0013153047
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note
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The RAMO was considered to point towards the surface of the protein in ref 18. The full calculation of the active-site region provides the correct orientation of the RAMO with respect to the protein structure.
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note
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Some additional factors further lower the distorting force in the tetrathiolate. The electrostatic charge model should be redistributed within the ligand, and the model assumes that only a single distorting mode is consequential.
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72
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0013109183
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note
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Recent studies have suggested that structural rearrangement of the active site could be sufficient to allow direct access to the iron. The crystallographic data used to support this proposal show a water molecule near the active site but still ∼4 Å away from the iron itself. The water is in close contact with one of the surface cysteinates and would ultimately allow for effective solvent-mediated electron transfer through the cysteinate ligand.
-
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73
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0013060403
-
-
note
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The importance of the H-bond pathways can be seen by recalculating the rate constant using the CEM structure where the active-site H-bonds have been broken. In this case, the rate constant drops by approximately 30%.
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