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H2O2 reactivity of a dinuclear copper(II) complex incorporating a constrained binucleating polyaminopyridyl ligand and a phosphodiester coligand
Gnana Sutha Siluvai, Babu Vargheese,
Published in
Volume: 375
Issue: 1
Pages: 93 - 100
A dinuclear copper(II) complex [Cu2(PD)(DPP-) 2](ClO4)2 (1) incorporating a constrained binucleating hexadenate ligand, PD (1,3-bis{bis[(2-pyridyl)ethyl]amino}benzene), and coligand, DPP- (diphenylphosphate) was synthesized and characterized, with a specific outlook towards evaluating spectroscopic and H2O2 reactivity relevant to the active-sites of noncoupled dinuclear copper enzymes, DβM and PHM. In solution, complex 1 exhibits a broad 1H NMR in the range -25 to +60 ppm and has a solution magnetic moment (μ) of ∼2.0 B.M./Cu(II), typical of a noninteracting dicopper(II) center. The room temperature H2O2 reactivity of 1 monitored by UV-Vis spectroscopy reveals the formation of a copper(II)-dioxygen intermediate 1a, which in turn leading to a arene ligand hydroxylation (PD-O-) and thus provide a new doubly-bridged dicopper(II) complex, [Cu2(PD-O-)(DPP-)](ClO4) 2 (2). The dioxygen intermediate produces OPPh3 on treatment with PPh3 revealing it is an electrophilic hydroperoxide oxidant. Solution magnetic moment of 1.61 B.M./Cu(II) indicates the product complex 2 is a moderately interacting dicopper(II) center and its 1H NMR spans between -20 and +180 ppm. A comparison of the optical absorption features of complex 1a with related dinuclear hydroperoxo-copper(II) complexes is discussed. © 2011 Elsevier B.V.
About the journal
JournalInorganica Chimica Acta
Open AccessNo