Table 4.
Comparison of experimental and calculated parameters for 1edt
| twist-ap | twist-bas | flat-ap | flat-bas | exp | |
|---|---|---|---|---|---|
| ΔE, kcal/mol | 5.73 | 5.76 | 2.03 | 0.00 | - |
| 57Fe, Fe1a) | |||||
| Aiso (MHz) | −0.55 | +0.97 | −4.59 | −4.74 | −8.30 |
| Adip (MHz) | +11.14 | +9.64 | +15.97 | +16.58 | +12.45 |
| Arh | +0.68 | +0.99 | +0.46 | +0.35 | + 0.70 |
| ΔEQ (mm/s)b) | +1.47 | −1.17 | −0.41 | −0.49 | −0.58 |
| η | 0.87 | 0.87 | 0.91 | 0.97 | 0.90 |
| δ (mm/s)c) | +0.15 | +0.14 | +0.17 | +0.16 | +0.20 |
| Mulliken | 0.7448 | 0.7023 | 0.9740 | 1.0189 | |
| 57Fe, Fe2a) | |||||
| Aiso (MHz) | −0.57 | 0.55 | −2.25 | −1.99 | −1.16 |
| Adip (MHz) | +5.77 | +7.17 | +2.02 | +1.43 | +0.90 |
| Arh (MHz) | +0.64 | +0.79 | +0.30 | +0.23 | +0.82 |
| ΔEQ (mm/s)b) | +0.70 | −0.59 | +0.67 | +0.80 | +0.70 |
| η | 0.99 | 0.69 | 0.52 | 0.48 | 0.92 |
| δ (mm/s)c) | −0.03 | −0.01 | +0.01 | +0.01 | +0.04 |
| Mulliken | 0.3946 | 0.4178 | 0.1147 | 0.0797 | |
| 31P(dppv), Aiso (MHz) | |||||
| P1 | −66.85 | −60.13 | −85.17 | −82.29 | −74.3 |
| P2 | −60.78 | −58.69 | −84.39 | −85.70 | −76.6 |
| 31P(PMe3), Aiso (MHz) | |||||
| P3 | +8.15 | −40.22 | +6.10 | −11.91 | −9.70 |
a)
Aiso - isotropic part, Adip - magnitude of the anisotropic part, Arh - rhombicity of anisotropic part, i.e. degree of deviation from axial character as such: A = Aiso + Adip[−1+Arh, −1−Arh, 2]
b)
As the asymmetry parameter is almost 100% the sign of ΔEQ does not have a physical meaning
c)
δ = 0.1181 − 0.3821 (ρ (0) − 11614), see Materials and Methods.