Ir-Catalyzed C-H Amidation and Borylation of Anthraquinones.

A mild, regioselective, iridium-catalyzed C-H amidation and borylation of anthraquinones to the o-sulfonamide and m-borylated products has been developed. The anthraquinone carbonyl moieties direct the C-H amidation with high selectivity to afford the ortho-substituted products in modest to high yields.

Copper(I)-phenolate complexes as models of the reduced active site of galactose oxidase: synthesis, characterization, and O2 reactivity.

The Cu(I)-phenolate complexes (1)LCu and (2)LCu and the Cu(I)-phenol complex [H(2)LCu(CNC(6)H(3)Me(2))]BArF(4) were prepared and structurally characterized by X-ray crystallography, where (1)L(-) and (2)L(-) are ligands comprised of a 2,4-di- tert-butylphenolate linked to 1-isopropyl-1,5-diazacyclooctane or 1,4-diisopropyl-1,4,7-triazacyclononane, respectively. The reduced galactose oxidase (GAO) structural models (1)LCu and (2)LCu were found to be highly reactive with O(2), and through combined stopped-flow kinetic and EPR, UV-vis, and resonance Raman spectroscopic studies of the oxygenation of (2)LCu at low temperature, new intermediates relevant to those postulated for the active site oxidation step of the GAO catalytic cycle were identified. The oxygenation was shown by kinetics experiments to proceed via initial binding of O(2) to yield a green, unusually thermodynamically stable 1:1 adduct, (2)LCu(O(2)).

Copper chemistry of beta-diketiminate ligands: monomer/dimer equilibria and a new class of bis(mu-oxo)dicopper compounds.

A series of Cu(I) and Cu(II) complexes of a variety of beta-diketiminate ligands (L(-)) with a range of substitution patterns were prepared and characterized by spectroscopic, electrochemical, and, in several cases, X-ray crystallographic methods. Specifically, complexes of the general formula [LCuCl](2) were structurally characterized and their magnetic properties assessed through EPR spectroscopy of solutions and, in one instance, by variable-temperature SQUID magnetization measurements on a powder sample. UV-vis spectra indicated reversible dissociation to 3-coordinate monomers LCuCl in solution at temperatures above -55 degrees C.

Three-coordinate copper(II)-phenolate complexes.

The reactions of LCuCl (L = 2,4-bis((2,6-diisopropylphenyl)imido)pentane (L(iPr)), 2,4-bis((2,6-diisopropylphenyl)imido)-3-chloropentane (L(CliPr))) with the phenolates TlOAr (Ar = C(6)H(3)Me(2), C(6)H(4)OMe, C(6)H(4)tBu) and NaOC(6)H(3)(tBu)(2) were explored. Novel three-coordinate Cu(II)-phenolates, LCuOAr, were isolated from the reactions with the thallium phenolates and were characterized by X-ray crystallography and spectroscopy (UV-vis, EPR). The complexes feature short Cu-O(phenolate) distances (average Cu-O = 1.

[Effect of Corynebacterium parvum preparation on selected immunologic indicators and clinical results in patients with chronic post-traumatic osteomyelitis].

Nineteen patients with chronic post-traumatic staphylococcal osteitis++ of a mean 5-years-clinical course were given intramuscularly 3.5 mg of Coparvax for two weeks. An increase of IgG concentration in the serum, starting from the 8th week of observation, and a marked increase of the ability of absorbtion and destruction of staphylococci by the neutrophils of the peripheral blood have been found.