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Title: Iron(II)-catecholate complexes of a monoanionic facial <i style="">N<sub>3</sub></i> ligand: Structural and functional models of the extradiol cleaving catechol dioxygenases
Authors: Paria, Sayantan
Halder, Partha
Chakraborty, Biswarup
Paine, Tapan Kanti
Keywords: Bioinorganic chemistry
Oxidative cleavage
Issue Date: Mar-2011
Publisher: CSIR
Abstract: Two biomimetic iron(II)-catecholate complexes, [(Tp<sup>Ph2</sup>)Fe<sup>II</sup>(CatH)] (<b style="">1</b>) and [(Tp<sup>Ph2</sup>)Fe<sup>II</sup>(DBCH)] <b>(2)</b> (where Tp<sup>Ph2</sup> = hydrotris(3,5-diphenylpyrazole-1-yl)borate, CatH = monoanionic pyrocatecholate and DBCH = monoanionic 3,5-di-<i style="">tert</i>-butyl catecholate), have been isolated and characterized to study their reactivity towards dioxygen. The single-crystal X-ray structure of <b style="">(1)</b> reveals a high-spin iron(II) center ligated by the monoanionic facial <i style="">N</i><i style=""><sub>3</sub></i> ligand and a monoanionic catecholate, giving rise to a trigonal bipyramidal coordination geometry. Complex <b style="">(1)</b> represents the first structurally characterized five-coordinate iron(II)-catecholate complex with an asymmetric bidentate binding motif of monoanionic catecholate. While <b style="">(1)</b> reacts with dioxygen to form the corresponding iron(III)-catecholate, <b style="">(2)</b> reacts with dioxygen to give 75 % extradiol and 25 % intradiol cleavage products via an iron(III)-catecholate intermediate species. Complex <b style="">(2)</b> is a potential functional model of extradiol cleaving catechol dioxygenases.
Description: 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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