X-band electron spin resonance (ESR) and electronic spectra of oxalatobridged heterodinuclear Cu-Ni and Cu-Zn complexes, viz., [(PMDT)Cu-Ox-Ni(PMDT)](BPh(4))(2).2CH(3)CN and [(PMDT)Cu-Ox-Zn(PMDT)](BPh(4))(2).2CH(3)CN, where PMDT=pentamethyldiethylenetriamine, Ox=oxalate ion have been described. Complex [(PMDT)Cu-Ox-Ni(PMDT)](BPh(4))(2).2CH(3)CN has been structurally characterized. This complex ...

The mechanistic details associated with the generation and reaction of [CuO]+ species from CuI-[alpha]-ketocarboxylate complexes, especially with respect to modifications of the ligand supporting the copper center, were investigated (see scheme). Theoretical models were used to characterize the electronic structures of different [CuO]+ species and their reactivity in C—H activation and O-atom t...

The reaction of oleanane triterpenoid 1b with a FeIII(PA; picolinate)3/H2O2/MeCN system (reagent system A), a simple model system for mono-oxygenase, gave the 11 alpha-hydroxyl derivative 3 as major product, along with 11-oxo derivative 4 and 12-oxo derivative 6. The reaction of lupane triterpenoid 2b with reagent system A gave only oxidative rearrangement compounds, (20R)-aldehyde 8 and (20S)-...

Copper bromide complexes with the ligands TMG6NO2qu, TMG6Brqu, TMG6Methoxyqu, TMG6NMe2qu, TMG6EHOqu and TMG6dBAqu were examined regarding their activity in atom transfer radical polymerization (ATRP). The inspired by 1,1,3,3-tetramethyl-2-(quinolin-8-yl)guanidine (TMGqu) substituents have been chosen a large range between electron withdrawing donating abilities. donor properties of can be stron...

The Cu3O4 layer in Sr2Cu3O4Cl2 is a variant of the square CuO2 lattice of the high-temperature superconductors, in which the center of every second plaquette contains an extra Cu2+ ion. The ions that make up the conventional CuO2 network, called CuI, have CuI-CuI exchange energy ≈130meV, and order antiferromagnetically at about 380 K; the CuII-CuII exchange is only ≈10meV, and the CuII’s order ...

We anticipate high-valent metal–fluoride species will be highly effective hydrogen atom transfer (HAT) oxidants because of the magnitude H−F bond (in product) that drives HAT oxidation. prepared a dimeric FeIII(F)−F−FeIII(F) complex (1) by reacting [FeII(NCCH3)2(TPA)](ClO4)2 (TPA=tris(2-pyridylmethyl)amine) with difluoro(phenyl)-λ3-iodane (difluoroiodobenzene). 1 was sluggish oxidant, however, ...

Complex formation and liquid-liquid extraction were studied in systems containing iron(III), 4-nitrocatechol (4NC),tetrazolium salt (TZS), water and organic solvent. Three different TZS were used: 3-(4,5-dimethyl-2-thiazol)-2,5-diphenyl-2H-tetrazolium bromide (MTT), 3-(2-naphtyl)-2,5diphenyl-2H-tetrazolium chloride (Tetrazolium violet, TV) and 2-(4-iodophenyl)-3-(4-nitrophenyl)5-phenyl-2H-tetra...

Understanding the properties of synthetic copper-oxygen intermediates is important for evaluating mechanisms of oxidations by enzymes and other catalysts.1,2 A growing class of reactive copper-oxygen complexes have been isolated or identified spectroscopically to date, including well-studied examples with [Cu2(O2)], [Cu2(μ-O)2], or [CuO2] cores.3 Mononuclear copperoxo species ([CuII-O-• T CuIII...