Manganese complexes as models for manganese-containing pseudocatalase enzymes: Synthesis, structural and catalytic activity studies

摘要

Manganese complexes of the type [TpMn(X)] and [TpMn(mu-N-3)(mu-X)MnTp] (X=acetylacetonate, acac; picolinate, pic and Tp=Tp(Ph,Me) for acac, Tp=Tp(ipr2) for pic complexes) having Tp(Ph,Me) (hydrotris(3-phenyl,5-methyl-pyrazol-1-yl)borate)/Tp(ipr2) (hydro-tris(3,5-diisopropyl-pyrazol- 1-yl)borate) as a supporting ligand have been synthesized and structurally characterized. IR and X-ray structures suggest that complexes 7 and 9 are binuclear with azido and bidentate ligands (acac/pic) bridging, whereas complexes 6 and 8 are mononuclear with a 5-coordinated metal center. In complex 9 the picolinate is coordinated as tridentate in a eta(3)-fashion, but in complex 7 acac behaves as bidentate, whereas azide is coordinated in a bridging bidentate mu-1,3-manner in both 7 and 9. Since the coordination geometry of the manganese ions in complex 9 is very similar to the active site structure of manganese-containing pseudocatalase, we have tested the catalytic activity of the same towards the disproportionation of hydrogen peroxide. The catalytic results indicated that complex 9 has reasonably good catalase activity and may be suitable, structurally as well as functionally, as a model for the pseudocatalase enzyme. (c) 2007 Elsevier Ltd. All rights reserved.