Table 1.
Spin Hamiltonian Parameters, Equation 1, of FeIII Species in H200C and Intermediates of H200Na
| Intermediate | D1 (cm−1) | (E/D)1 | J (cm−1) | ΔEq (mm/s) | η | a1[x,y,z] (T) | δ (mm/s) | Ref. |
|---|---|---|---|---|---|---|---|---|
| H200C-HPCAInt1 HPCA•-FeIII-OO(H) |
+ 1.2(2) | 0.05(3) | > +40 | −0.97(1)d | 0.55 | −21.0(2) −21.5(2) −21.6(1) |
0.48(1) | This work |
| H200N-HPCAInt1 HPCA•-FeIII-OO(H) |
+ 1.1 | 0.12 | +25(5) | −0.95b | 0b | −21.5 −21.5 −21.5 |
0.48 | 24 |
| H200N-4NCInt2 4NC•-FeIII-OO(H) |
+0.67 | 0.11 | +40(10) | −0.87 | 0.8 | −21.5 −21.5 −21.5 |
0.49 | 22 |
| H200N-4NCInt1 4NC-FeIII-O2• |
−0.59 | 0.20 | +6(2) | −0.33 | −3 | −21.4 −21.4 −21.4 |
0.50 | 22 |
| H200C-HPCAInt1 (S=2 representation) |
+1.6c | 0.05(3) | - | −0.97 | 0 | −24.5 −25.1 −25.2c |
0.48 | This work |
a
Spectra of the H200N-4NCInt1, the spin coupled high-spin FeIII-superoxo complex of H200N; H200N-4NCInt2, the spin coupled high-spin semiquinone-FeIII-peroxo complex of H200N.
b
Spectra of the H200N-HPCAInt1 were of much lower quality; η and the quoted angles (α = γ = 0, β = 90°) are rather approximate.
c
The quantities quoted are D = (4/3)D1, (E/D)= (E/D)1 and A1 = (7/6)a1.
d
The EFG is rotated by Euler angles α = 58°, β = 70°, γ = 50° relative to the ZFS tensor; see text.