Catechols copper complexes

Granata, A., Monzani, E. and Casella, L. (2004), Mechanistic insight into the catechol oxidase activity by a biomimetic dinuclear copper complex, J. Biol. Inorg. Chem., 9, 903-913. 

Terminally metallizable dyes (30) are obtained by the interaction of a diazonium salt and a coupling component containing a chelating system, for example salicylic acid, catechol, salicyl-aldoxime or 8-hydroxyquinoline, and their coordination chemistry is typical of these compounds. Such dyes were rarely used as preformed metal complexes but were usually applied to cotton and then converted to their copper complexes on the fibre to improve their fastness to wet treatments. A typical example is the blue dyestuff (31). 

Adamic and Bartak [6] used high pressure aqueous size exclusion chromatography with reverse pulse amperometric detection to separate copper(II) complexes of poly(amino carboxylic acids), catechol and fulvic acids. The commercially available size exclusion chromatography columns were tested. Columns were eluted with copper(II) complexes of poly(aminocarboxylic acids), citric acids, catechol and water derived fulvic acid. The eluent contained copper(II) to prevent dissociation of the labile metal complexes. Reverse pulse electrochemical measurements were made to minimise oxygen interferences at the detector. Resolution of a mixture of DTP A, EDTA and NTA copper complexes was approximately the same on one size exclusion chromatography column as on Sephadex... 

Cu2(L )(NCS)2] (66), which has been shown (c.f. Fig. 8) [43] to contain two tetrahedrally coordinated Cu(I) ions held 2.796(8) A apart and linked inter-molecularly via the sulfur atoms of the thiocyanate ions. For the complexes 63 and 64, the reduction product is the diamagnetic complex [Cu2(L )(MeCN)2](Y)2 (67) (Y = CIO4 or BPh4) in which each three coordinate Cu(I) ion is bonded to two of the four macrocyclic nitrogen atoms and to the nitrogen of one of the two MeCN molecules (Fig, 9) [43]. In the presence of certain substrates the reduction of 63 or 64 is accompanied by substrate oxidation. For example, PhSH, PhC=CH, hydrazobenzene, catechols, hydroquinone, and ascorbic acid afford PhSSPh, PhC=CCsPh, azobenzene, o-quinones, p-quinone, and dehydroascorbic acid, respectively, together with the reduced species 67 and/or other copper complexes... 

Figure 3 Binuclear copper complexes in octopus hemocyanin (a) and sweet potato catechol oxidase (b) showing the thioether linkage between a cysteine residue and a directly coordinating histidine imidazole. Heteroatoms (N,0,S) are indicated by a shaded quadrant. [ortep-III views based on PDB ID 1JS8 and IBTl]...

Copper complexation was evaluated by ligand exchange with catechol and cathodic stripping voltammetry of the copper-catechol complexes (28, 29). Titration curves with Cu were obtained by spiking aliquots of lake-water samples with different Cu concentrations. The free [Cu2 ] concentration was calculated from the concentration of copper-catechol complexes formed in equilibrium with free catechol. 

Fig. 4. Ligands used for biomimetic copper complexes of tyrosinase and catechol oxidase.

Complexes of cyclodextrin modified with catechol groups 75 proved to be less active in phenol hydroxylation the main product was catechol and the selectivity with respect to this product exceeded 90%. For copper complexes... 

The nickel(IV) oxime, bis(6-amino-3-methyl-4-azahexa-3-ene-2-one oxime)nickel(IV), and the nickel(III) oxime, (15-amino-3-methyl-4,7,10,13-tetraazapentadeca-3-ene-2-one oxime)nickel(III), complexes react with hydro-quinone. Proton-related equilibria for both the nickel complexes and the hydroquinone could be elucidated from the kinetic details. For reactions with the complexes and the hydroquinone could be elucidated from the kinetic details. For reactions with the Ni(III) complex there is evidence of an inner-sphere process. The [NiL(TCCat)] complex (TCCatH2 = tetrachlorocatechol L = 2,4,4-trimethyl-1,5,9-triazacyclododec-l-ene) forms a 1 1 adduct with tetrachloro-1,2-benzoquinone. Spectroscopic evidence suggests that this compound can be described formally as a quinone adduct of a Ni(I)-semiquinone moiety arising from inner-sphere ligand oxidation. The crystallographically determined structure (11) is shown below. Several copper complexes of a vareity of semiquinones also exist in solution in equilibrium with the corresponding catechol complexes. ... 

The oxidation of substituted o-diphenols to the corresponding o-benzoquinones in the presence of 4 different binuclear copper complexes has been investigated by Bolus and Vigee [14]. The initial rates of oxidation were within a factor of 4 for the substrates catechol, 4-methylcatechol, dopamine, 3,4-dihydroxybenzoic acid, and 3,4-dihydroxybenzonitrile. The ligands of the catalyst complexes were Schiff-base type derivatives of 2,6-diformyI-4-methylphenol with diamines and amino acids their synthesis and characterization have been reported [15]. 

Two new ligands N,N-bis(3,5-dimethylpyrazol-l-ylmethyl)benzylamine, bpmba, and N,N,N, N tetrakis(3,5-dimethylpyrazol-l-ylmethyl)-a,a -diamino-/n-xylene. bpmdx have recently been synthesized [26] their copper complexes are active catalysts for the oxidation of catechol to 0 benzoquinone. 

Tyrosinase-catalyzed transformations of catechols and o-benzoquinones were modeled by copper complexes which mimic both the spectroscopic characteristics [44-48] and the chemical behavior [49,50] of the biological systems. Tyrosinases have so-called copper type 3 centers, which are strongly antiferromagnetically coupled. The multicopper concept has emerged as an important feature in the modeling approach. 

The development of catalysts for the efficient oxidation of catechol and its derivatives in water is topic of ongoing work in this laboratory. Towards this end, polyethylene glycol side-chains were incorporated in a pentadentate salen ligand to enhance the water solubility of the complexes derived thereof. A dinuclear copper(II) complex is found to catalyze the oxidation of 3,5-di-tert.-butylcatechol into 3,5-di-tert-butyl-o-benzoquinone more than twice as fast in aqueous organic solution as in purely organic solvents (ly,at/knon= 140,000). Preliminary data are discussed. 

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