Characterization of the mixed axial ligand complex (4-cyanopyridine)(imidazole)(tetramesitylporphinato)iron(iii) perchlorate. Stabilization by synergic bonding

Abstract

The reaction of [Fe(TMP)(OClO[Formula: see text]], where TMP is the dianion of tetramesitylporphyrin, with a combination of a strong [Formula: see text]-acceptor ligand and a [Formula: see text]-donating imidazole can lead to the preparation of mixed-ligand complexes [Fe(Porph)(4-CNPy)(L)][Formula: see text] where L is imidazole itself or 1-acetylimidazole and 4-cyanopyridine is the strong [Formula: see text] acceptor ligand. The stability of the new mixed-ligand pair is the presumed result of synergic bonding between the two axial ligands. The molecular structure and other characterization of the new mixed axial ligand complex, [Fe(TMP)(4-CNPy)(HIm)]ClO4 is described. The axial ligands have a relative perpendicular arrangement with Fe–N(imidazole) = 1.945 Å and Fe–N(pyridine) = 2.021 Å. The average equatorial Fe–N[Formula: see text] distance is 1.963 Å, which is consistent with the S4-ruffled TMP core. Despite the relative perpendicular arrangement of axial ligands, the EPR spectrum of the complex is a rhombic signal and not a large gmax signal. The EPR g-values are [Formula: see text] 3.05, [Formula: see text] 2.07, and [Formula: see text] 1.22. A quadrupole doublet was seen in the Mössbauer spectrum with an isomer shift of 0.197 mm/s and quadrupole splitting of 1.935 mm/s. Two crystalline forms of [Fe(TMP)(4-CNPy)(HIm)]ClO4 have been characterized; the two forms differ only in the solvent content of the lattice. Crystal data for form A: [Formula: see text] 15.432 (12) Å, [Formula: see text] 20.696 (2) Å, [Formula: see text] 19.970 (5) Å, and [Formula: see text] 99.256 (14)[Formula: see text], monoclinic, space group P21/n, V [Formula: see text] 6295 (2) Å3, Z [Formula: see text] 4, formula FeCl3O4N8C[Formula: see text]H[Formula: see text], 8397 observed data, [Formula: see text] 0.086, [Formula: see text] 0.210, refinement on [Formula: see text]. Crystal data for form B: [Formula: see text]15.267 (3) Å, [Formula: see text]20.377 (6) Å, [Formula: see text] 19.670 (4) Å, and [Formula: see text] 98.14 (1)[Formula: see text], monoclinic, space group P[Formula: see text]/n, V = 6058 (4) Å3, Z = 4, formula C[Formula: see text]H[Formula: see text]Cl[Formula: see text]FeN8O4, 5464 observed data, [Formula: see text] 0.096, [Formula: see text] 0.112, refinement on F.