Table 2.
Key orbital components for the DFT calculations of Fe(II)- [Fe(tpp)(ImH)2] and Fe(III)- [Fe(tpp)(ImH)2]+. MO diagrams of tpp and ImH are given in the Supporting Information, Figure S2 and S3. Bold numbers indicate the orbital number from the ADF calculation.
| Main contribution to MO | Fe(II)-heme | Fe(III)-heme |
|---|---|---|
| Fe(dx2-y2) | 81. 67%(Fe-dx2-y2) + 27%(6b2g-tpp) + 4%(tpp-other) | 77. 61%(Fe-dx2-y2) + 29%(tpp-6b2g) + 6%(Fe-dz2). |
| Fe(dz2) | 76. 65%(Fe-dz2) + 9%(tpp-a1g) + 2%(tpp-other)+ 18%(ImH-12) + 6%(ImH-other). | 76. 59%(Fe-dz2) + 20%(ImH-12) + 8%(tpp-a1g) + 5%(Fe-dx2-y2) |
| Heme π-acceptor (4eg(D4h)) | 75. 90%(tpp-4eg) + 9%Fe(dyz/dxz) | 75. 94%(tpp-4eg) + 6%(Fe-dyz) 74. 95%(tpp-4eg) + *3%(Fe-dxz) |
| Fe(dxz/dyz) | 73. 81%(Fe-dxy+dxz) + 6%(tpp-4eg) + 2%(ImH-other)+ 5%(tpp-other) 72. 83%(Fe-dxy+dxz) + 7%(tpp-4eg) + 4%(tpp-other) | 73. 70%(Fe-dyz) + 20%(tpp-3eg) + 2%(tpp-4eg) 3%(ImH-11) 72. 71%(Fe-dxz) + 22%(tpp-3eg) + 2%(tpp-4eg) |
| Fe(dxy) | 71. 75%(Fe-dyz) + 15%(tpp-3eg) + 6%(tpp-4eg) + 5%(tpp-other) | 71. 93%Fe(dxy) |
| Heme π-donor (3eg(D4h)) | 69. 56%(tpp-3eg) + 22%(tpp-52Ag) + 7%(Fe-dyz) + 11%(tpp-other) +7%(Fe-dxz/dyz/dxy) | 64. 71%(tpp-3eg) + 19%(Fe-dyz) |
| Heme σ-donor (6b1g(D4h))** | 60. 50%(tpp-6b2g) + 22%(Fe-dx2-y2) + 12%(tpp-41Ag) + 14%(tpp-other)+ 3%(ImH-other) | 55. 36%(tpp-41ag) + 34%(tpp-6b2g) + 15%(Fe-dx2-y2) + 7%(tpp-45 Ag) |
| Heme σ-donor (7a1g(D4h))93 | 56. 33%(tpp-7a1g) + 22%(tpp-42ag) + 18%(Fe-dz2) + 18%(ImH-12ag) +5%(tpp-other) | 52. 38%(tpp-7a1g) + 23%(Fe-dz2) + 15%(ImH-12ag) 50. 33%(tpp-42ag) 16%(tpp-40ag) + 16%(tpp-6b2g) + 10%(Fe-dx2-y2) + 2 %(Fe-dz2) |
**
x and y axes bisect the N-Fe-N bonds.