Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating reactivities of oxygen-containing metal complexes in a variety of biological and biomimetic reactions, including dioxygen activation/formation and functionalization of organic substrates. Mononuclear nonheme iron(III)-peroxo species are invoked as active oxygen intermediates in the catalytic cycles of dioxyg...

We report direct electrochemistry of the iNOS heme domain in a DDAB film on the surface of a basal plane graphite electrode. Cyclic voltammetry reveals FeIII/II and FeII/I couples at -191 and -1049 mV (vs Ag/AgCl). Imidazole and carbon monoxide in solution shift the FeIII/II potential by +20 and +62 mV, while the addition of dioxygen results in large catalytic waves at the onset of FeIII reduct...

Abstract: The anionic polymerization of 1-phosphaisoprene [Mes*P=C(Me)−CH=CH2 (E-1)] affords poly(1-phosphaisoprene) 2 in high yield (75%). Concentrated solutions polymer (Mn = 21,800 g mol–1; Đ 1.02) a P-analogue natural rubber, undergo gelation upon treatment with [Pd(cod)Cl2] (0.15 P equiv). Evidence for P-coordination to PdII was obtained by 31P and 1H NMR spectroscopy. is reversed the addi...

High-valent oxoiron(iv) porphyrin p-cation radicals 2 are generally accepted to be the key reactive intermediates in a variety of oxidation reactions by heme-containing enzymes such as cytochromes P450, peroxidases, and catalases.[1,2] Extensive studies with synthetic iron(iii) porphyrin complexes and various terminal oxidants have shown that 2 is generated by heterolytic O X bond cleavage of [...

In a previous paper some of us presented the structure and properties new family ionic liquids, ILs, with common cation, 1-butyl-3-methyl imidazolium (the popular [C4C1Im]+ or [BMIM]+) variety anions based in thiocyanate (SCN)−: one reference sample ten anionic metal complexes different valences: AlIII, MnII, FeIII, CrIII, NiII, HgII, ZnII, CoII CuI, resulting, respectively, [BMIM](SCN), [BMIM]...

Presented herein is a study of the acid-induced demetalation of two sterically hindered copper corroles, Cu β-octabromo-meso-triphenylcorrole (Cu[Br8TPC]) and β-octakis(trifluoromethyl)-meso-tris(p-methoxyphenyl)corrole (Cu[(CF3)8TpOMePC]). Unlike reductive demetalation, which affords the free-base β-octabromocorrole, demetalation of Cu[Br8TPC] under non- reductive conditions (CHCl3/H2SO4) resu...

Two polyanions [SeI V2 PdII4 WVI14 O56 H]11- and [SeI V4 PdII4 WVI28 O108 H12 ]12- are the first hybrid polyoxometalates in which classical (Group 5/6 metal based) and non-classical (late transition-metal based) polyoxometalate units are joined. Requiring no supporting groups, this co-condensation of polyoxotungstate and isopolyoxopalladate constituents also provides a logical link between POM-...