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Mimicking the Intradiol Catechol Cleavage Activity of Catechol Dioxygenase by High-Spin Iron(III) Complexes of a New Class of a Facially Bound [N(2)O] Ligand

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Title Mimicking the Intradiol Catechol Cleavage Activity of Catechol Dioxygenase by High-Spin Iron(III) Complexes of a New Class of a Facially Bound [N(2)O] Ligand
 
Creator PANDA, MK
JOHN, A
SHAIKH, MM
GHOSH, P
 
Subject nonheme iron enzymes
functional models
protocatechuate 3,4-dioxygenase
crystal-structures
cleaving dioxygenases
tridentate ligands
catalytic-activity
substrate complex
binding-site
3n ligands
 
Description A series of high-spin iron(III) complexes, {N-R-2-[(pyridin-2-ylmethyl)amino]acetamide}FeCl(3) [R = mesityl (1b), 2,6-Et(2)C(6)H(3) (2b), and 2,6-i-Pr(2)C(6)H(3) (3b)], that functionally emulate the intradiol catechol dioxygenase enzyme are reported. In particular, these enzyme mimics, 1b, 2b, and 3b, which utilized molecular oxygen in carrying out the intradiol catechol cleavage of 3,5-di-tert-butylcatechol with high regioselectivity. (ca. 81-85%) at room temperature under ambient conditions, were designed by employing a new class of a facially bound [N(2)O] ligand, namely, N-R-2-[(pyridin-2-ylmethyl)amino]acetamide [R = mesityl (1a), 2,6-Et(2)C(6)H(3) (2a), and 2,6-i-Pr(2)C(6)H(3) (3a)]. The density functional theory studies revealed that the intradiol catechol cleavage reaction proceeded by an iron(III) peroxo intermediate that underwent 1,2-Criegee rearrangement to yield the intradiol catechol cleaved products analogous to the native enzyme.
 
Publisher AMER CHEMICAL SOC
 
Date 2011-07-14T11:58:51Z
2011-12-26T12:48:22Z
2011-12-27T05:34:41Z
2011-07-14T11:58:51Z
2011-12-26T12:48:22Z
2011-12-27T05:34:41Z
2008
 
Type Article
 
Identifier INORGANIC CHEMISTRY, 47(24), 11847-11856
0020-1669
http://dx.doi.org/10.1021/ic801576f
http://dspace.library.iitb.ac.in/xmlui/handle/10054/3947
http://hdl.handle.net/10054/3947
 
Language en