Structural and spectroscopic studies of a model for catechol oxidase

JBIC Journal of Biological Inorganic Chemistry - Tập 13 - Trang 499-510 - 2008
Sarah J. Smith1, Christopher J. Noble2, Randahl C. Palmer2, Graeme R. Hanson2, Gerhard Schenk1, Lawrence R. Gahan1, Mark J. Riley1
1School of Molecular and Microbial Sciences, The University of Queensland, St. Lucia, Australia
2Centre for Magnetic Resonance, The University of Queensland, St Lucia, Australia

Tóm tắt

A binuclear copper complex, [Cu2(BPMP)(OAc)2][ClO4]·H2O, has been prepared using the binucleating ligand 2,6-bis[bis(pyridin-2-ylmethylamino)methyl]-4-methylphenol (H-BPMP). The X-ray crystal structure reveals the copper centers to have a five-coordinate square pyramidal geometry, with the acetate ligands bound terminally. The bridging phenolate occupies the apical position of the square-based pyramids and magnetic susceptibility, electron paramagnetic resonance (EPR) and variable-temperature variable-field magnetic circular dichroism (MCD) measurements indicate that the two centers are very weakly antiferromagnetically coupled (J = −0.6 cm−1). Simulation of the dipole–dipole-coupled EPR spectrum showed that in solution the Cu–O–Cu angle was increased from 126° to 160° and that the internuclear distance was larger than that observed crystallographically. The high-resolution spectroscopic information obtained has been correlated with a detailed ligand-field analysis to gain insight into the electronic structure of the complex. Symmetry arguments have been used to demonstrate that the sign of the MCD is characteristic of the tetragonally elongated environment. The complex also displays catecholase activity (k cat = 15 ± 1.5 min−1, K M = 6.4 ± 1.8 mM), which is compared with other dicopper catechol oxidase models.

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