Isocyanide or nitrosyl complexation to hemes with varying tethered axial base ligand donors: synthesis and characterization

Article abstract of DOI:10.1007/s00775-016-1369-4

Abstract: A series of ferrous-heme 2,6-dimethylphenyl isocyanide (DIMPI) and ferrous-heme mononitrosyl complexes have been synthesized and characterized. The heme portion of the complexes studied is varied with respect to the nature of the axial ligand, including complexes, where it is covalently tethered to the porphyrinate periphery. Reduced heme complexes, [(F₈)Fe^II], [(P^Py)Fe^II], [(P^Im)Fe^II], and [(P^ImH)Fe^II], where F₈?=?tetrakis(2,6-difluorophenyl)-porphyrinate and P^Py, P^Im, and P^ImH are partially fluorinated tetraaryl porphyrinates with covalently appended axial base pyridyl/imidazolyl or histamine moieties, were employed; P^ImH is a new construct. Room temperature addition of DIMPI to these iron(II) complexes affords the bis-isocyanide species [(F₈)Fe^II-(DIMPI)₂] in the case of [(F₈)Fe^II], while for the other hemes, mono-DIMPI compounds are obtained, [(P^Py)Fe^II-(DIMPI)] [(2)-DIMPI], [(P^Im)Fe^II-(DIMPI)] [(3)-DIMPI], and [(P^ImH)Fe^II-(DIMPI)] [(4)-DIMPI]. The structures of complexes (3)-DIMPI and (4)-DIMPI have been determined by single crystal X-ray crystallography, where interesting H…F(porphryinate aryl group) interactions are observed. ¹⁹F-NMR spectra determined for these complexes suggest that H…F(porphyrinate aryl groups) attractions also occur in solution, the H atom coming either from the DIMPI methyl groups or from a porphyinate axial base imidazole or porphyrinate pyrrole. Similarly, we have used nitrogen monoxide to generate ferrous-nitrosyl complexes, a five-coordinate species for F₈, [(F₈)Fe^II-(NO)], or low-spin six-coordinate compounds [(P^Py)Fe^II-(NO)], [(P^Im)Fe^II-(NO)], and [(P^ImH)Fe^II-(NO)]. The DIMPI and mononitrosyl complexes have also been characterized using UV–Vis, IR, ¹H-NMR, and EPR spectroscopies. Graphical abstract: [Figure not available: see fulltext.]