Table 1.
B3LYP free energies (including dielectric effects) in kcal/mol for the splitting of the spin states in the reactant [Fe2(μ-O)2(TPA)2(ClO4)]2+(complex 1) and [Fe2(μ-O)(O)(H2O)(TPA)2(ClO4)]2+ (complex 2) as well as for the intermediate resulting after hydrogen abstraction. (a) The energy of the intermediates is set in relation to the reactant ground state.
| Reactant | ΔE | Intermediate | ΔEa | ||||||
|---|---|---|---|---|---|---|---|---|---|
| Fe1(III) | Fe2(IV) | S | Complex 1 | Complex 2 | Fe1(III) | Fe2(III) | S | Complex 1 | Complex 2 |
| 1α |
2α 2β |
3/2 1/2 |
9,5 6,4 |
11,5 12,7 |
1α |
1α 1β |
1 0 |
12,6 10,6 |
18 18,5 |
|
4α 4β |
5/2 3/2 |
0,7 0,6 |
8,6 9,3 |
3α 3β |
2 1 |
14,6 13,0 |
20,4 23,8 |
||
| 3α |
2α 2β |
5/2 1/2 |
11,9 8,2 |
14.7 - |
5α 5β |
3 2 |
7,0 10,4 |
6,4 7,4 |
|
|
4α 4β |
7/2 1/2 |
10,7 - |
8,8 9,5 |
3α |
3α 3β |
3 0 |
21,5 - |
29.5 - |
|
| 5α |
2α 2β |
7/2 3/2 |
1,2 2,0 |
1,2 4,5 |
5α 5β |
4 1 |
12,4 12,4 |
13,3 12,4 |
|
|
4α 4β |
9/2 1/2 |
2,0 0,0 |
0,9 0 |
5α |
5α 5β |
5 0 |
3,7 2,3 |
-1,2 -2,6 |
|