Table 3. NPA Partial Charges for Selected Atoms in the 2+ and 1+ Complexesa.
| B3LYP/6-311+G(d,p) |
M06/6-311+G(d,p) | LC-BLYP/def2-TZVP | CAM-B3LYP/6-311+G(d,p) | |||
|---|---|---|---|---|---|---|
| atom | 2+ | 1+ | 1+ | 1+ | 1+ | |
| ligand | Ru | 0.160 | 0.161 | 0.144 | 0.069 | 0.139 |
| bpy (1st) | N | –0.379 | –0.389 | –0.400 | –0.401 | –0.453 |
| N | –0.379 | –0.389 | –0.399 | –0.401 | –0.453 | |
| bpy (2nd) | N | –0.379 | –0.388 | –0.400 | –0.310 | –0.371 |
| N | –0.379 | –0.389 | –0.399 | –0.303 | –0.361 | |
| bpy (3rd) | N | –0.379 | –0.388 | –0.400 | –0.310 | –0.371 |
| N | –0.379 | –0.388 | –0.399 | –0.303 | –0.361 | |
a
Note the similar charges on the Ru atom in the overall 1+ and 2+ complexes, indicating that the added electron is on the ligands. Note also the asymmetric charge distribution over the three ligands with the long-range corrected functionals as compared to the symmetric distribution using B3LYP and M06.