Table 3.
Selected Structural Parameters of Six-coordinate [Co(Por)(L)2] Complexesa
| Complex | Δ24b | (Co–Np)av | Co–Lfifthc | Co-LSixthd | ϕfifthe | ϕsixthe | θf | ref. |
|---|---|---|---|---|---|---|---|---|
| Co(II) complexes | ||||||||
| [Co(II)(TPP)(pip)2] (2-fold) | 0.00 | 1.987(2) | 2.436(2) | 2.436(2) | – | – | – | 34 |
| [Co(II)(OEP)(3-MePy)2] (2-fold) | 0.00 | 1.992(1) | 2.386(2) | 2.386(2) | 12.03 | 12.03 | 0.00 | 35 |
| Co(III) complexes | ||||||||
| [Co(III)(α,α,β,β-TpivPP)(2-MeHIm)(2-MeIm−)] | 0.00 | 1.934(5) | 1.972(3) | 1.953(3) | 43.4 | 34.3 | 80.2 | tw |
| [Co(III)(α,α,β,β-TpivPP)(2-MeHIm)(2-MeIm−)] (mol 1) | −0.03 | 1.943(5) | 1.972(3) | 1.957(3) | 36.6 | 33.1 | 71.2 | tw |
| [Co(III)(α,α,β,β-TpivPP)(2-MeHIm)(2-MeIm−)] (mol 2) | 0.05 | 1.951(4) | 1.957(3) | 1.952(3) | 37.7 | 44.4 | 85.7 | tw |
| [Co(III)(TPP)(HIm)2]OAc g | 0.00 | 1.982(11) | 1.945(15) | 1.945(15) | 43 | 43 | 0 | 36 |
| [Co(III)(TDCPP)(1-MeIm)2]BF4 | 0.01 | 1.977(5) | 1.942(5) | 1.941(6) | 11.2 | 10.0 | 89.8 | 37 |
a
Distances in Å, Angles in deg., tw = this work.
b
Displacement of the metal atom from the 24-atom mean plane, a positive number indicates a displacement toward the imidazole ligand.
c
Bond distance between iron atom and imidazole (pip, Py) nitrogen atom.
d
Bond distance between iron atom and the coordinate atom of sixth ligand.
e
Dihedral angle between the planes defined by the closest Np–Co–Nim/im– and the imidazole or imidazolate plane.
f
Dihedral angle between the planes defined by two axial ligand planes.
g
The data is cited for one of the two half-porphyrins in the asymmetric unit.