Table 5.
Mulliken Spin Densities and Compositions of Spin-Down Molecular Orbitals (%) Involved in Fe=O Bonding Based on PBE0 DFT Computations for Select [FeIV(O)(TMC)(X)]2+/+ (1-X) Complexes.
| Spin density | Fe dxz MO (β) | Fe dyz MO (β) | Fe dz2 MO (β) | ||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|
| Fe | O | Fe 3d | O 2p | X 2p | Fe 3d | O 2p | X 2p | Fe 3d | O 2p | X 2p | |
| 1-NCMe | 1.36 | 0.81 | 51 | 36 | 0.9 | 53 | 34 | 1.1 | 59 | 19 | 1.1 |
| 1-O2CCF3 | 1.48 | 0.71 | 59 | 32 | 1.9 | 62 | 32 | 1.3 | 59 | 18 | 1.9 |
| 1-N3 | 1.43 | 0.72 | 55 | 33 | 3.1 | 61 | 28 | 7.5 | 55 | 16 | 8.9 |
| 1′-SR | 1.42 | 0.75 | 53 | 37 | 0.9 | 62 | 27 | 5.5 | 56 | 15 | 8.6 |
| 1-CN | 1.37 | 0.82 | 53 | 36 | 3.9 | 55 | 35 | 4.1 | 57 | 15 | 2.6 |