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Calix[6]tren and copper(II): a third generation of funnel complexes on the way to redox calix-zymes.

ABSTRACT: Mono-copper enzymes play an important role in biology and their functionality is based on Cu(II)/Cu(I) redox processes. Modeling a mono-nuclear site remains a challenge for a better understanding of its intrinsic reactivity. The first member of a third generation of calixarene-based mono-copper "funnel" complexes is described. The ligand is a calix[6]arene capped by a tren unit, hence presenting a N(4) coordination site confined in a cavity. Its Cu(II) complexes were characterized by electronic and EPR spectroscopies. The x-ray structure of one of them shows a five-coordinated metal ion in a slightly distorted trigonal bipyramidal geometry thanks to its coordination to a guest ligand L (ethanol). The latter sits in the heart of the hydrophobic calixarene cone that mimics the active site chamber and the hydrophobic access channel of enzymes. Competitive binding experiments showed a preference order dimethylformamide > ethanol > MeCN for L binding at the single exchangeable metal site. Cyclic voltammetry studies showed irreversible redox processes in CH(2)Cl(2) when L is an oxygen donor caused by the redox-driven ejection of the guest at the Cu(I) level. In the presence of MeCN, a pseudoreversible process was obtained, owing to a fast equilibrium between a four and a five-coordinate Cu(I) species. Finally, a redox-driven ligand interchange of dimethylformamide for MeCN at the Cu(I) state allowed the trapping of the thermodynamically less stable Cu(II)-MeCN adduct. Hence, this work represents an important step toward the elaboration of a functional supramolecular model for redox mono-copper enzymes, named redox calix-zymes.

SUBMITTER: Izzet G

PROVIDER: S-EPMC1100775 | biostudies-literature | 2005 May

REPOSITORIES: biostudies-literature

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Calix[6]tren and copper(II): a third generation of funnel complexes on the way to redox calix-zymes.

Izzet Guillaume G Douziech Bénédicte B Prangé Thierry T Tomas Alain A Jabin Ivan I Le Mest Yves Y Reinaud Olivia O

Proceedings of the National Academy of Sciences of the United States of America 20050502 19

Mono-copper enzymes play an important role in biology and their functionality is based on Cu(II)/Cu(I) redox processes. Modeling a mono-nuclear site remains a challenge for a better understanding of its intrinsic reactivity. The first member of a third generation of calixarene-based mono-copper "funnel" complexes is described. The ligand is a calix[6]arene capped by a tren unit, hence presenting a N(4) coordination site confined in a cavity. Its Cu(II) complexes were characterized by electronic ...[more]

PMID: 15867151

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Calix[6]tren and copper(II): a third generation of funnel complexes on the way to redox calix-zymes.

Publications

Calix[6]tren and copper(II): a third generation of funnel complexes on the way to redox calix-zymes.

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