Table 2.
Total contributions (%) of unoccupied fragment molecular orbitals (UFOs) to the occupied orbitals of [ML(SC6F5)], the resulting charge transfer (a.u.) from the SC6F5- thiolate to the ML+ fragment, and the NPA spin density sNPA (a.u.) on the thiolate ligand in the complexes.
| Mn | Fe | Co | Ni | Cu | Zn | |
|---|---|---|---|---|---|---|
| Donation (SC6F5−→ ML+) | ||||||
| % (α-spin UFO of ML+) | 29.5 | 29.6 | 28.2 | 28.2 | 26.2 | 32.5 |
| % (β-spin UFO of ML+) | 32.0 | 33.6 | 48.9 | 47.3 | 81.7 | 32.5 |
| Back-donation (SC6F5− ← ML+) | ||||||
| % (α-spin UFO of SC6F5−) | 3.1 | 3.5 | 3.5 | 3.4 | 4.3 | 2.7 |
| % (β-spin UFO of SC6F5−) | 2.7 | 4.8 | 4.2 | 3.7 | 4.0 | 2.7 |
| ΔqNPA (SC6F5− → ML+) | 0.32 | 0.36 | 0.38 | 0.37 | 0.57 | 0.28 |
| sNPA (SC6F5−) | 0.13 | 0.16 | 0.17 | 0.16 | 0.38 | 0.00 |