Structural and spectroscopic studies of a model for catechol oxidase.
A binuclear copper complex, [Cu2(BPMP) (OAc)2][ClO4] x 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 degrees to 160 degrees 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.
Smith
Sarah J
SJ
School of Molecular and Microbial Sciences, The University of Queensland, St Lucia, QLD 4072, Australia.
Noble
Christopher J
CJ
Palmer
Randahl C
RC
Hanson
Graeme R
GR
Schenk
Gerhard
G
Gahan
Lawrence R
LR
Riley
Mark J
MJ
D002384:Catalysis; D004156:Catechol Oxidase / Q000737:chemistry* / Q000378:metabolism; D002942:Circular Dichroism; D003300:Copper / Q000737:chemistry; D018360:Crystallography, X-Ray; D008024:Ligands; D008280:Magnetics; D008958:Models, Molecular; D013053:Spectrophotometry; D013696:Temperature
D008024:Ligands; D003300:Copper; D004156:Catechol Oxidase