Table 2.
Calculated Fe-Fe and Fe-ligand distances (Å), net spin populations (NSP) of Fe1(III), Fe2(IV) and Tyr122·, broken symmetry state energies E (eV), 57Fe Mössbauer isomer shift (δ, mm s−1), quadrupole splittings (ΔEQ, mm s−1) and η, and proton hyperfine coupling constants (Axx, Ayy, Azz, MHz) for Tyr122· in models X(di-μ-oxo)-Asp84H-Tyr122· and X(μ-oxo)(μ-hydroxo)-Tyr122· in wild-type and in W48F variant, and compared with experimental (exp) results
| Wild-type | W48F | ||||
|---|---|---|---|---|---|
| X(di-μ-oxo)- Asp84H-Tyr122· |
X(μ-oxo)(μ- hydroxo)-Tyr122· |
X(di-μ-oxo)- Asp84H-Tyr122· |
X(μ-oxo)(μ- hydroxo)-Tyr122· |
exp a | |
| Fe1-Fe2 | 2.724 | 2.912 | 2.749 | 2.909 | |
| Fe1-O1 | 1.860 | 1.928 | 1.877 | 1.928 | |
| Fe2-O1 | 1.777 | 1.712 | 1.758 | 1.712 | |
| Fe1-O2 | 1.942 | 2.049 | 1.949 | 2.046 | |
| Fe2-O2 | 1.735 | 1.927 | 1.744 | 1.957 | |
| Fe1-O3 | 2.097 | 2.191 | 2.119 | 2.174 | |
| Fe1-N-His118 | 2.252 | 2.196 | 2.255 | 2.162 | |
| Fe2-N-His241 | 2.145 | 2.153 | 2.143 | 2.169 | |
| Fe1-O-Asp84 | 2.817 | 2.014 | 2.495 | 1.999 | |
| Fe1-O-Glu115 | 1.963 | 1.975 | 1.973 | 2.006 | |
| Fe2-O-Glu115 | 2.591 | 2.454 | 2.603 | 2.246 | |
| Fe2-O-Glu204 | 1.957 | 1.914 | 1.961 | 1.916 | |
| Fe2-O-Glu238 | 2.094 | 2.032 | 2.100 | 2.063 | |
| NSP(Fe1) | 4.01 | 4.07 | 4.02 | 4.07 | |
| NSP(Fe2) | −3.23 | −3.28 | −3.24 | −3.29 | |
| NSP(C1-Tyr122·) | −0.39 | −0.39 | −0.39 | −0.39 | |
| NSP(C2-Tyr122·) | 0.09 | 0.10 | 0.10 | 0.10 | |
| NSP(C3-Tyr122·) | −0.22 | −0.24 | −0.22 | −0.23 | |
| NSP(C4-Tyr122·) | −0.05 | −0.03 | −0.04 | −0.03 | |
| NSP(O-Tyr122·) | −0.30 | −0.31 | −0.30 | −0.31 | |
| NSP(C5-Tyr122·) | −0.25 | −0.25 | −0.25 | −0.26 | |
| NSP(C6-Tyr122·) | 0.10 | 0.10 | 0.10 | 0.11 | |
| E | −880.5871 | −880.7229 | −849.8933 | −850.0994 | |
| δ(Fe1, Fe2) | (0.50, 0.22) | (0.51, 0.31) | (0.52, 0.21) | (0.51, 0.32) | (0.47, 0.22) |
| ΔEQ(Fe1, Fe2) | (0.54, −0.33) | (−0.43, −0.64) | (0.46, −0.35) | (0.54, −0.59) | (−0.7, −0.64) |
| η(Fe1, Fe2) | (0.77, 0.66) | (0.53, 0.44) | (0.76, 0.80) | (0.88, 0.42) | (0.5, 2.7) |
| 1H(Axx, Ayy, Azz) for Tyr122·: | |||||
| H-3 | (23.9, 6.8, 19.4) | (25.1, 7.6, 20.0) | (24.2, 6.9, 19.6) | (24.6, 7.3, 19.7) | (26.9, 7.8, 19.6) |
| H-5 | (26.1, 7.1, 21.0) | (26.3, 7.6, 21.3) | (26.2, 7.0, 21.0) | (27.2, 7.6, 21.9) | (26.9, 7.8, 19.6) |
| H-β1 | −(69.6, 62.9, 64.5) | −(80.9, 74.2, 75.9) | −(73.2, 66.6, 68.1) | −(69.5, 63.1, 64.6) | (57.8, 52.1, 54.9) |
| H-2 | −(6.4, 0.7, 3.1) | −(6.7, 1.2, 3.5) | −(6.5, 0.8, 3.9) | −(6.8, 1.2, 3.5) | ~( 0, 0, 0) |
| H-6 | −(6.5, 0.6, 3.0) | −(6.8, 1.0, 3.5) | −(6.6, 0.6, 3.1) | −(7.0, 1.2, 3.7) | ~( 0, 0, 0) |
| H-β2 | (−3.8, 1.3, 0.9) | −(11.6, 6.0, 6.9) | (−4.8. −0.09, 0.4) | (−4.4, 0.3, 0.9) | ~ (0, 0, 0) |
| H-link | −(57.4, 50.5, 52.0) | −(36.5, 30.5, 31.7) | −(52.8, 46.1, 47.6) | −(53.9, 47.3, 48.8) | |
a
Experimental data are for W48F mutant E. coli R2, taken from Ref. 12.