Copper complex with

Making and breaking the dioxygen 0—0 bond with participation of synthetic copper complexes with heterocyclic ligands 97ACR227. 

Photoprocesses of RNA-bound copper complexes with macroheterocyclic ligands 98CRV1201. 

Six coordinate copper complexes with gii < g in the solid state. I. Bertini, D. Gatteschi and... 

Kensler, T.W. and Trush, M.A, (1983). Inhibition of oxygen radical metabolism in phorbol ester-activated polymorphonuclear leukocytes by an antitumor promoting copper complex with superoxide dismutase-mimetic activity. Biochem. Pharmacol. 32, 3485-3487. 

Fig. 10.6. Dimeric (Ar = 2,6-dimethylphenyl) (a) and monomeric (Ar = 2,4,6-trimethylphenyl) (b) copper complexes with diphenylcarbene. Reproduced from J. Am. Chem. Soc., 126, 10085 (2004), by permission of the American Chemical Society.

Many examples of asymmetric reactions catalyzed by copper complexes with chiral ligand systems have been reported. In particular, various copper-bis(oxazoline) catalysts (e.g., complexes (H) to (L), Scheme 48) are effective for carbon-carbon bond-forming reactions such as aldol,204 Mukaiyama-Michael, Diels-Alder,206 hetero Diels-Alder,207,208 dipolar cycloaddition,209,210... 

Figure 33 The bisarene copper complex with S-cylindrophane 80. Reproduced with permission from Wiley.

Moi, M.K., Meares, C.F., McCall, M.J., Cole, W.C., and DeNardo, S.J. (1985) Copper chelates as probes of biological systems stable copper complexes with a macrocyclic bifunctional chelating agent. Anal. Biochem. 148, 249-253. 

ARGET ATRP has been successfully applied for polymerization of methyl methacrylate, ft-butyl acrylate and styrene in the presence of Sn(EH)2 (10 mol% vs. alkyl halide initiator or 0.07 mol% vs. monomer) [164,165]. For all monomers, polymerizations were well controlled using between 10 and 50 ppm of copper complexes with highly active TPMA and Me6TREN ligands. ARGET ATRP has also been utilized in the synthesis of block copolymers (poly(n-butyl acrylate)— -polystyrene and polystyrene-Z -poly(n-butyl acrylate) [164,165] and grafting... 

The subject molecules are obtained as dinuclear copper complexes with the octa-aza cryptate ligands L1 and L2 shown in Scheme 1. 

Copper complexes with organic acids from landfill leachates were contributing to the toxicity towards zebra fish embryos only if the molar mass of the complexes was sufficiently small to allow penetration of biological membranes [228]. Fractions of landfill leachate with M > 5000 g mol-1 had a... 

A lipophilic copper complex with neocuproine has been found to increase the toxicity of a trichlorophenol in bacteria, probably due to increased transport of Cu over the membrane [229],... 

Palmer, F. B., Butler, C. A., Timperley, M. H. and Evans, C. W. (1998). Toxicity to embryo and adult zebrafish of copper complexes with two malonic acids as models for dissolved organic matter, Environ. Toxicol. Chem., 17, 1538-1545. 

The reaction of binuclear copper complexes with oxygen as models for tyrosinase activity was also markedly accelerated by applying pressure (106408 ). Tyrosinase is a dinuclear copper protein which catalyses the hydroxylation of phenols. This reaction was first successfully modeled by Karlin and co-workers (109), who found that an intramolecular hydroxylation occurred when the binuclear Cu(I) complex of XYL-H was treated with oxygen (Scheme 5). 

Special consideration should be paid to metal complexes such as azomethine pigments (Sec. 2.10). At high temperatures, the yellow copper complex with the chemical constitution 10, incorporated in PVC, will exchange its chelated copper atoms with the metal atoms present in the application medium. Stabilizers containing barium/cadmium or lead produce yellow shades, while dibutyl tin thiogly-colate or other tin compounds produce a brilliant medium red. Color change is slow at low temperatures, but at 160°C the effect is rapid [108],... 

In the following sections we shall discuss (i) the structure and behaviour of the various copper complexes with the ligands listed in scheme 2 (ii) the activities of the polymeric catalysts in comparison with the low molecular weight analogs (iii) the effect of the degree of substitution, a, on the activities of the polymeric catalysts. 

The basic study was performed on copper complexes with N,N,N, N1-tetramethylethane-1,2-diamine (TMED), which were known to be very effective oxidative coupling catalysts (7,12). From our first kinetic studies it appeared that binuclear copper complexes are the active species as in some copper-containing enzymes. By applying the very strongly chelating TMED we were able to isolate crystals of the catalyst and to determine its structure by X-ray diffraction (13). Figure 1 shows this structure for the TMED complex of basic copper chloride Cu(0H)Cl prepared from CuCl by oxidation in moist pyridine. 

Another related example can be found in the series of copper complexes with the bis(imino)-3-formyl-l-phenyl-pyridinethione ligands shown in Scheme 18.180 Both Cu(I) and Cu(II) complexes can be prepared with this type of ligands. 

Decomposition of the copper complex with HjS in acid leads to allothreonine and (in about 2-fold excess) threonine. Following the pioneering work of Akabori et this reaction has been extended to a variety of metals and aldehydes and to complexes such as A- and A-Co(en)2gly with intriguing stereoselectivity behavior (optically-active allothreonine and threonine products). ... 

More advanced semiempirical molecular orbital methods have also been used in this respect in modeling, e.g., the structure of a diphosphonium extractant in the gas phase, and then the percentage extraction of zinc ion-pair complexes was correlated with the calculated energy of association of the ion pairs [29]. Semiempirical SCF calculations, used to study structure, conformational changes and hydration of hydroxyoximes as extractants of copper, appeared helpful in interpreting their interfacial activity and the rate of extraction [30]. Similar (PM3, ZINDO) methods were also used to model the structure of some commercial extractants (pyridine dicarboxylates, pyridyloctanoates, jS-diketones, hydroxyoximes), as well as the effects of their hydration and association with modifiers (alcohols, )S-diketones) on their thermodynamic and interfacial activity [31 33]. In addition, the structure of copper complexes with these extractants was calculated [32]. 

Hathaway has attempted to assess the value of the electronic properties of polycrystalline mononuclear copper complexes with the [CUN4], [CuNj], and [CuN ] chromophores of unknown crystal structure, in predicting the stereochemical environment of the copper(ii) atom. The value of having B. J. Hathaway, J.C.5. Dalton, 1972, 1196. 

Upon acylation of the copper complex with benzoyl chloride the corresponding 5-benzoylthio-1,2,3,4-thiatriazole is formed. The reaction product is (apparently) incorrectly assigned by the authors to 4-benzoyl-1,2,3,4-thiatriazole-5-thione based upon comparison with the product obtained from direct acylation of thiatriazol-5-thiol and citation of the older incorrect structure assignments. The thiothiatriazolato-copper(I) complexes are formulated as Cu-N(4) complexes. However, this assignment is based upon an IR band at 1200 cm attributed to a thiocarbonyl group, again upon comparison with the older literature. Further characterization therefore seems necessary. 

The most active system to date for the Cu-catalyzed oxidation of cyclohexane has only recently been reported. Reaction of triethanolamine with Cu(N03)2 in the presence of NaOH and different types of aromatic carboxy-lates, NaNs or NaBp4 yielded a family of multinuclear copper complexes with different structural characteristics, including 6 and 7. These systems showed... 

Dinudear copper complexes with aliphatic tripodal amino alcohol ligands were tested in the oxidation of DTBC (Eq. 17) [221]. It was shown that... 

A. Kandegedara, Ph.D. Dissertation, Electron-Transfer Kinetics of Copper Complexes with Macrocyclic Terdentate Ligands, Wayne State University, 2001. 

A group at the Academy of Sciences in Moscow 197) has synthesized chiral threonine. Derivatives of cyclic imino acids form copper complexes with glacine and carbonyl compounds. Hydroxyethylation with acetaldehyde and decomposition of the resulting complexes produced threonine with an optical purity of up to 97-100% and with threo/allo ratios of up to 19 1 197). The chiral reagents could be recovered and re-used without loss of stereoselectivity. The mechanism of this asymmetric synthesis of amino acids via glacine Schiff base/metal complexes was also discussed 197). 

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