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3543104606
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∈ and Δ∈ are given per Mn(III)/Mn(III) dimer of OxMnCAT
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∈ and Δ∈ are given per Mn(III)/Mn(III) dimer of OxMnCAT.
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48
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3543098918
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49
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3543054319
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Mansucript in preparation
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-1 band appears to be much sharper than in solution spectra recorded at room temperature. This is due to strong antiferromagnetic exchange interactions in the corresponding excited state and will be discussed elsewhere. Brunold, T. C.; Gamelin, D. R.; Solomon, E. I. Mansucript in preparation.
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3543115236
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note
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2O the molecular x′, y′, and z′ axes coincide with the crystallographic c, a, and b axes, respectively.
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3543048568
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Previous calculations in ref 47b have focused on calculating ground-state exchange coupling constants and charge and spin densities
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(a) Previous calculations in ref 47b have focused on calculating ground-state exchange coupling constants and charge and spin densities.
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57
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0001242382
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61
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3543101163
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note
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-1) can be eliminated for two reasons: (i) Jahn-Teller distortions in Mn(III) complexes will ensure a sufficiently large separation of the single unoccupied d orbital from the occupied orbitals and (ii) the low-lying excited state would spin-orbit couple to the ground state, giving rise to an imbalance between positive and negative MCD intensity.
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68
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3543083623
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note
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-1 (azide bound form). While the absolute D values have little meaning, their positive signs and similar magnitudes underline the high resemblance of the two data sets.
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3543104605
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The sign change does not require that D passes through O: Along the Berry pseudorotation coordinate, E increases to maximum rhombicity and a reorientation of the coordinate system is required
-
The sign change does not require that D passes through O: Along the Berry pseudorotation coordinate, E increases to maximum rhombicity and a reorientation of the coordinate system is required.
-
-
-
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76
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3543098917
-
-
Note that this represents the effective electronic symmetry for the Mn ions and does not rule out distortion along a coordinate leading toward square pyramidal geometry
-
Note that this represents the effective electronic symmetry for the Mn ions and does not rule out distortion along a coordinate leading toward square pyramidal geometry.
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77
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3543054318
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note
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AH calculations performed on the OxMnCAT and MnSOD models afforded a monodentate carboxylate based HOMO mainly localized on the noncoordinating oxygen atom. In the protein this orbital will be stabilized by hydrogen bonding interactions, and it has therefore been omitted in the analysis of the computational results.
-
-
-
-
80
-
-
3543135059
-
-
note
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2-based unoccupied spin-down MO is stabilized relative to the other Mn d-based unoccupied spin down MOs (Figure 9) due to substantial delocalization onto Mn2 and/or mixing with the Mn 4s orbital.
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81
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0029738010
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note
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3,72
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0041117418
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89
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3543097758
-
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note
-
The quality of the fit (obtained under the assumption that the bandwidths do not change upon azide binding) suffers from large band distortions arising from spin-orbit coupling between the quintet and triplet LF excited states.
-
-
-
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90
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0029944136
-
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Addition of azide to MnSOD at 295 K results in a five-coordinate complex that interconverts to a six-coordinate species at low temperatures. This change in coordination number is accompanied by a decrease in integrated intensity of about 50%. Whittaker, M. M.; Whittaker, J. M. Biochemistry 1996, 35, 6762.
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3543078968
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note
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-1. In view of the simplicity of this model the correspondence is satisfactory.
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It is noteworthy that Mn catalase isolated from T. thermophilus undergoes complete autoxidation to the Mn(III)/Mn(III) level and that pH influences the rate but not the extent of oxidation. Khangulov, S. V.; Barynin, V. V.; Antonyuk-Barynina, S. V. Biochim. Biophys. Acta 1990, 1020, 25.
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+/Fc, +0.55 V correction factor. Que, L., Jr.; True, A. E. In Progress in Inorganic Chemistry: Bioinorganic Chemistry; Lippard, S. J., Ed.; Wiley: New York, 1990; p 181.
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2(III/ III) reduction potentials are identical
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2(III/ III) reduction potentials are identical.
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(a) Pessiki, P. J.; Khangulov, S. V.; Ho, D. M.; Dismukes, G. C. J. Am. Chem. Soc. 1994, 116, 891.
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The proton-coupled one-electron reduction potential of methemerythrin is E° = +110 mV. Armstrong, F. A.; Harrington, P. C.; Wilkins, R. G. J. Inorg. Biochem. 1983, 18, 83.
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