Skip to main content

Table 2 Uranium organic complex potential energies (Hartrees/molecule), interatomic distances (in Å) and calculated 13C NMR chemical shifts (in ppm).

From: Quantum mechanical calculation of aqueuous uranium complexes: carbonate, phosphate, organic and biomolecular species

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
  1. 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)
  2. 1 = One U-OH2 deprotonated to form U-OH and a H3O+ in the solvation sphere
  3. 2 = One U-O at 1.85 Å and one U-OH at 1.96 Å
  4. 3 = One U-OH at 2.14 Å and one U-OH at 2.21 Å
  5. 4 = aqueous Gibbs free energy in the quintet structure without ZPE correction