Mononitrosyl-iron compounds (MNICs) of the Enemark-Feltham {FeNO} type can be divided into a doublet (S=1/2) and a quartet (S=3/2) spin variant. The latter relies on weak-field co-ligands such as amine carboxylates. Aqua-only co-ligation appears to exist in the long-known "brown-ring" [Fe(H O) (NO)] cation, which was prepared originally from ferrous salts and NO in sulfuric acid.
View Article and Find Full Text PDFTyrosinase model systems pinpoint pathways to translating Nature's synthetic abilities for useful synthetic catalysts. Mostly, they use N-donor ligands which mimic the histidine residues coordinating the two copper centres. Copper complexes with bis(pyrazolyl)methanes with pyridinyl or imidazolyl moieties are already reported as excellent tyrosinase models.
View Article and Find Full Text PDFA set of (3,3')-bis(1-Ph-2-R-1H-2,1-benzazaborole) compounds, in which R=tBu (Bab-tBu) , R=Dipp (Bab-Dipp) or R=tBu and Dipp (Bab-Dipp)(Bab-tBu), was synthesized and fully characterized using H, B, C, and N NMR spectroscopy as well as single-crystal X-ray diffraction analysis. The central HC(sp )-C(sp )H bond with restricted rotation at the junction of both 1H-2,1-benzazaborole rings displayed an intriguing reactivity. It was demonstrated that this bond is easily mesolytically cleaved using alkali metals to form the respective aromatic 1Ph-2R-1H-2,1-benzazaborolyl anions M (THF) (Bab-tBu) (M=Li, Na, K) and K (THF) (Bab-Dipp) .
View Article and Find Full Text PDFBis(pyrazolyl)methane ligands are excellent components of model complexes used to investigate the activity of the enzyme tyrosinase. Combining the N donors 3-tert-butylpyrazole and 1-methylimidazole results in a ligand that is capable of stabilising a (μ-η(2) :η(2) )-dicopper(II) core that resembles the active centre of tyrosinase. UV/Vis spectroscopy shows blueshifted UV bands in comparison to other known peroxo complexes, due to donor competition from different ligand substituents.
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