Table 2.
Selected geometrical and electronic properties of the FeM and FeM2 compounds 5–8, 10 and 11. Gibbs free energies refer to formation reactions, where the corresponding metal ions react with chloride ions and the corresponding free ligands. GAP is the energy difference of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).
| 5 | 6 | 7 | 8 | 10 | 11 | |
|---|---|---|---|---|---|---|
| d(P=N) | 1.650 | 1.616 | 1.659 | 1.623 | 1.654 | 1.618 |
| d(M-Cl) | 2.256 | 2.285 | 2.258 | 2.283 | 2.258 | 2.283 |
| ΔrG [kJmol−1] | −1797b | −701b | −1824 | −711 | −1811 | −708 |
| GAP [eV] | 3.34 | 4.55 | 2.91 | 4.35 | 4.08 | 4.58 |
| ν(P=N) [cm−1]a | 948b (940) | 953b (923) | 948 (940) | 957 (929) | 942 (930) | 951 (930) |
| ν(M-Cl) [cm−1]a | 374;385 (382 br) | 345;357 (331;349) | 370;384 (384 br) | 344;357 (331;347) | 371;384 (359 br) | 343;358 (331;351) |
a
IR spectra were simulated in aqueous solvent; (experimental values obtained from nujol mulls between polyethylene sheets).
b
For the doubly substituted complexes, the reaction energies were scaled per metal atom.