New heme-dioxygen and carbon monoxide adducts using pyridyl or imidazolyl tailed porphyrins.
Inspired by the chemistry relevant to dioxygen storage, transport and activation by metalloproteins, in particular for heme/copper oxidases, and carbon monoxide binding to metal-containing active sites as a probe or surrogate for dioxygen binding, a series of heme derived dioxygen and CO complexes have been designed, synthesized, and characterized with respect to their physical properties and reactivity. The focus of this study is in the description and comparison of three types heme-superoxo and heme-CO adducts. The starting point is in the characterization of the reduced heme complexes, [(F8)FeII], [(PPy)FeII] and [(PIm)FeII], where F8, PPyand PImare iron(II)-porphyrinates and where PPyand PImpossess a covalently tethered axial base pyridyl or imidazolyl group, respectively. The spin-state properties of these complexes vary with solvent. The low temperature reaction between O2and these reduced porphyrin FeIIcomplex yield distinctive low spin heme-superoxo adducts. The dioxygen binding properties for all three complexes are shown to be reversible, via alternate argon or O2bubbling. Carbon monoxide binds to the reduced heme-FeIIprecursors to form low spin heme-CO adducts. The implications for future investigations of these heme O2and CO adducts are discussed.
Department of Chemistry, The Johns Hopkins University, Baltimore, MD 21218.
Yuqi
Y
Li
Savita K
SK
Sharma
Kenneth D
KD
Karlin
1,2H-NMR spectroscopy; Base tethered heme complexes; Heme-FeIII-superoxo complexes; Reduced Heme-FeII complexes; heme-FeII-carbonyl complexes