Structural and spectroscopic studies of a model for catechol oxidase

Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry
Sarah J SmithMark J Riley

Abstract

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(c...Continue Reading

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Citations

Dec 10, 2008·The Journal of Chemical Physics·Andrew DickMark J Riley
Oct 10, 2015·Inorganic Chemistry·Gayan B WijeratneJoshua Telser
Jul 15, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Shaban Y ShabanRudi van Eldik
Dec 17, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Salah S MassoudFranz A Mautner
Jan 29, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Samit MajumderSasankasekhar Mohanta
Jun 22, 2013·Chemical Reviews·Scott E AllenMarisa C Kozlowski

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