Table 1. Dispersion Interaction Energies [kcal mol–1] of 2–6 Obtained Using the D3(BJ) Models for Structures Obtained with Six Different DFT Approaches in Conjunction with the def2-TZVPP Basis Set.
| BP86 | BP86-D3(BJ) | BP86-D4 | B3LYP | B3LYP-D3(BJ) | B3LYP-D4 | ||
|---|---|---|---|---|---|---|---|
| E[Fe···Cu2] | –1.01 | –1.03 | –1.02 | –0.96 | –0.97 | –0.96 | |
| 2 | E[Cu1–DIPP]a | –6.56 | –5.96 | –6.10 | –5.86 | –5.91 | –6.09 |
| E[Cu3A–DIPP]b | –6.02 | –6.22 | –6.30 | –5.32 | –5.71 | –5.78 | |
| E[Fe···Ag1] | –1.22 | –1.23 | –1.22 | –1.15 | –1.15 | –1.14 | |
| 3 | E[Ag2–DIPP]c | –7.41 | –7.52 | –7.62 | –6.62 | –7.06 | –7.18 |
| E[Ag2′–DIPP]d | –7.50 | –7.97 | –8.00 | –6.68 | –7.29 | –7.37 | |
| 4 | E[Fe···Cu1] | –1.01 | –1.00 | –1.00 | –0.96 | –0.95 | –0.095 |
| E[Cu2–DIPP]e | –6.32 | –6.81 | –6.74 | –5.34 | –6.08 | –6.20 | |
| 5 | E[Ag–DIPP]f | –6.55 | –7.39 | –7.42 | –5.77 | –6.75 | –6.88 |
| 6 | E[Au–DIPP]f | –6.74 | –8.50 | –8.37 | –5.73 | –6.08 | –6.08 |
The quasi-transparent Li(thf)3 moiety of 3 (Figure 3) indicates that the corresponding groups are half occupied in the solid phase. This would correspond to an asymmetric structure in the gas phase as used for the computations, where the Li(thf)3 group is only present on one side. This explains the asymmetry of the structure and the different values tabulated for the groups labeled with and without prime. (See Section 3 from Supporting Information).
DIPP moiety associated with the C19/C19’ carbon, see Figure 4. As discussed in the text, the gas-phase structures of complexes 5 and 6 used in the computations belong to the symmetry point group Ci, and therefore, the molecular groups with the same numbering but with prime are equivalent due to symmetry.