Table 2.
Uranium organic complex potential energies (Hartrees/molecule), interatomic distances (in Å) and calculated 13C NMR chemical shifts (in ppm).
| Models | G | CN | U=O | U-O(H2) | U-O(C) | δ13C |
| Oxalate | ||||||
| Expt (This work) | ----- | --- | ----- | ----- | ----- | 174.5 |
| HOx-•8(H2O) | -989.3358 | --- | ----- | ----- | ----- | 176.2 |
| Ox2-•8(H2O) | -988.7157 | --- | ----- | ----- | ----- | 179.3 |
| Uranyl-oxalate | ||||||
| Expt (This work) | ----- | --- | ----- | ----- | ----- | 169.0 |
| [UO2(OH2)4]2+-Ox | -885.0151 | 7 | 1.79 | 2.61 | 2.28 | 164.7 |
| [UO2(OH2)4]2+-Ox•11(H2O) | -1725.8906 | 7 | 1.79 | 2.481 | 2.41 | 172.0 |
| [UO2(OH2)4]2+-Ox•30(H2O) | -3178.3494 | 7 | 1.79 | 2.47 | 2.40 | 167.4 |
| Catechol | ||||||
| Expt [102] | DMSO | --- | ----- | ----- | ----- | 116.1, 119.8, 145.6 |
| Solid | --- | ----- | ----- | ----- | 115.7, 121.7, 142.7 | |
| H2Cat | -382.6927 | --- | ----- | ----- | ----- | 115.5, 121.1, 144.3 |
| Uranyl-catechol | ||||||
| Expt (This work) | DMSO | 115.7, 119.3, 145.3 | ||||
| Solid | 115.7, 122.3, 143.4 | |||||
| [UO2(OH2)4]2+-H2Cat | -890.0170 | 8 | 1.76 | 2.62 | 2.60 | 116.1, 132.4, 137.7 |
| [UO2(OH2)4]2+-H2Cat (OS) | -3029.9112 | 7 | 1.79 | 2.45 | ≈5.9 | 115.7, 126.1 |
| 123.2, 128.6 | ||||||
| 138.5, 147.4 | ||||||
| [UO2(OH2)4]2+-H2Cat•28(H2O) (Singlet) | ||||||
| -3029.8947 | 7 | 1.79 | 2.45 | 2.48 | 121.8, 128.3, 141.6 | |
| [UO(OH)(OH2)4]2+-HCat•28(H2O) (Triplet) | ||||||
| -3029.9386 | 7 | 1.912 | 2.50 | 2.42 | 138.3, 179.1, 113.2, 114.2, 127.6, 128.3, |
|
| [U(OH)2(OH2)4]2+-Cat•28(H2O) (Quintet) | ||||||
| -3029.9477 | 7 | 2.173 | 2.43 | 2.60 | 192.0, 195.3 | |
| 129.4, 151.2 | ||||||
| 123.0, 137.1 | ||||||
| [U(OH)2(OH2)4]2+-Cat•28(H2O) (Singlet)4 | ||||||
| -3030.6937 | -- | ----- | ----- | ----- | 160.5, 181.6, | |
| 116.7, 144.5, | ||||||
| 149.6, 159.4 | ||||||
| [U(OH)2(OH2)4]2+-Quinone•28(H2O) (OS) | ||||||
| -3029.9359 | 7 | 2.17 | 2.46 | ≈6 | 114.9, 194.3 | |
| 137.7, 166.3 | ||||||
| 159.8, 202.6 | ||||||
δ13C relative to TMS HF/6-31G(d,p)//B3LYP/6-31G(d,p) chemical shielding of 201.4 and δ17O relative to water B3LYP/6-311+G(d,p)//B3LYP/6-31G(d,p) chemical shielding of 293 ppm. δ13C shifts listed in order as the two phenolic C atoms, the two C atoms α with respect to the phenol groups, and the two C atoms β with respect to the phenol groups. (OS = outer-sphere)
1 = One U-OH2 deprotonated to form U-OH and a H3O+ in the solvation sphere
2 = One U-O at 1.85 Å and one U-OH at 1.96 Å
3 = One U-OH at 2.14 Å and one U-OH at 2.21 Å
4 = aqueous Gibbs free energy in the quintet structure without ZPE correction