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Title: Iron(II)-catecholate complexes of a monoanionic facial N3 ligand: Structural and functional models of the extradiol cleaving catechol dioxygenases
Authors: Paria, Sayantan
Halder, Partha
Chakraborty, Biswarup
Paine, Tapan Kanti
Keywords: Bioinorganic chemistry;Iron;Oxidative cleavage;Catechol
Issue Date: Mar-2011
Publisher: CSIR
Abstract: Two biomimetic iron(II)-catecholate complexes, [(TpPh2)FeII(CatH)] (1) and [(TpPh2)FeII(DBCH)] (2) (where TpPh2 = hydrotris(3,5-diphenylpyrazole-1-yl)borate, CatH = monoanionic pyrocatecholate and DBCH = monoanionic 3,5-di-tert-butyl catecholate), have been isolated and characterized to study their reactivity towards dioxygen. The single-crystal X-ray structure of (1) reveals a high-spin iron(II) center ligated by the monoanionic facial N3 ligand and a monoanionic catecholate, giving rise to a trigonal bipyramidal coordination geometry. Complex (1) represents the first structurally characterized five-coordinate iron(II)-catecholate complex with an asymmetric bidentate binding motif of monoanionic catecholate. While (1) reacts with dioxygen to form the corresponding iron(III)-catecholate, (2) reacts with dioxygen to give 75 % extradiol and 25 % intradiol cleavage products via an iron(III)-catecholate intermediate species. Complex (2) is a potential functional model of extradiol cleaving catechol dioxygenases.
Page(s): 420-426
ISSN: 0975-0975(Online); 0376-4710(Print)
Appears in Collections:IJC-A Vol.50A(03-04) [March-April 2011]

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