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Dioxygen reactivity of biomimetic iron-catecholate and iron-o-aminophenolate complexes of a tris(2-pyridylthio)methanido ligand: aromatic C-C bond cleavage of catecholate versus o-iminobenzosemiquinonate radical formation.
Chemistry. 2012 Sep 10; 18(37):11778-87.C

Abstract

An iron(III)-catecholate complex [L(1)Fe(III)(DBC)] (2) and an iron(II)-o-aminophenolate complex [L(1)Fe(II)(HAP)] (3; where L(1) = tris(2-pyridylthio)methanido anion, DBC = dianionic 3,5-di-tert-butylcatecholate, and HAP = monoanionic 4,6-di-tert-butyl-2-aminophenolate) have been synthesised from an iron(II)-acetonitrile complex [L(1)Fe(II)(CH(3)CN)(2)](ClO(4)) (1). Complex 2 reacts with dioxygen to oxidatively cleave the aromatic C-C bond of DBC giving rise to selective extradiol cleavage products. Controlled chemical or electrochemical oxidation of 2, on the other hand, forms an iron(III)-semiquinone radical complex [L(1)Fe(III)(SQ)](PF(6)) (2(ox)-PF(6); SQ = 3,5-di-tert-butylsemiquinonate). The iron(II)-o-aminophenolate complex (3) reacts with dioxygen to afford an iron(III)-o-iminosemiquinonato radical complex [L(1)Fe(III)(ISQ)](ClO(4))(3(ox)-ClO(4); ISQ = 4,6-di-tert-butyl-o-iminobenzosemiquinonato radical) via an iron(III)-o-amidophenolate intermediate species. Structural characterisations of 1, 2, 2(ox) and 3(ox) reveal the presence of a strong iron-carbon bonding interaction in all the complexes. The bond parameters of 2(ox) and 3(ox) clearly establish the radical nature of catecholate- and o-aminophenolate-derived ligand, respectively. The effect of iron-carbon bonding interaction on the dioxygen reactivity of biomimetic iron-catecholate and iron-o-aminophenolate complexes is discussed.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Halder P
Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, 2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, India.
Paria S
No affiliation info available
Paine TK
No affiliation info available

MeSH

AminophenolsBenzoquinonesBiomimeticsCatecholsFerric CompoundsFerrous CompoundsLigandsModels, MolecularMolecular StructureOxygenPyridines

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

22847897

Citation

Halder, Partha, et al. "Dioxygen Reactivity of Biomimetic Iron-catecholate and Iron-o-aminophenolate Complexes of a Tris(2-pyridylthio)methanido Ligand: Aromatic C-C Bond Cleavage of Catecholate Versus O-iminobenzosemiquinonate Radical Formation." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 18, no. 37, 2012, pp. 11778-87.
Halder P, Paria S, Paine TK. Dioxygen reactivity of biomimetic iron-catecholate and iron-o-aminophenolate complexes of a tris(2-pyridylthio)methanido ligand: aromatic C-C bond cleavage of catecholate versus o-iminobenzosemiquinonate radical formation. Chemistry. 2012;18(37):11778-87.
Halder, P., Paria, S., & Paine, T. K. (2012). Dioxygen reactivity of biomimetic iron-catecholate and iron-o-aminophenolate complexes of a tris(2-pyridylthio)methanido ligand: aromatic C-C bond cleavage of catecholate versus o-iminobenzosemiquinonate radical formation. Chemistry (Weinheim an Der Bergstrasse, Germany), 18(37), 11778-87. https://doi.org/10.1002/chem.201200886
Halder P, Paria S, Paine TK. Dioxygen Reactivity of Biomimetic Iron-catecholate and Iron-o-aminophenolate Complexes of a Tris(2-pyridylthio)methanido Ligand: Aromatic C-C Bond Cleavage of Catecholate Versus O-iminobenzosemiquinonate Radical Formation. Chemistry. 2012 Sep 10;18(37):11778-87. PubMed PMID: 22847897.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Dioxygen reactivity of biomimetic iron-catecholate and iron-o-aminophenolate complexes of a tris(2-pyridylthio)methanido ligand: aromatic C-C bond cleavage of catecholate versus o-iminobenzosemiquinonate radical formation. AU - Halder,Partha, AU - Paria,Sayantan, AU - Paine,Tapan Kanti, Y1 - 2012/07/29/ PY - 2012/03/15/received PY - 2012/8/1/entrez PY - 2012/8/1/pubmed PY - 2013/1/9/medline SP - 11778 EP - 87 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 18 IS - 37 N2 - An iron(III)-catecholate complex [L(1)Fe(III)(DBC)] (2) and an iron(II)-o-aminophenolate complex [L(1)Fe(II)(HAP)] (3; where L(1) = tris(2-pyridylthio)methanido anion, DBC = dianionic 3,5-di-tert-butylcatecholate, and HAP = monoanionic 4,6-di-tert-butyl-2-aminophenolate) have been synthesised from an iron(II)-acetonitrile complex [L(1)Fe(II)(CH(3)CN)(2)](ClO(4)) (1). Complex 2 reacts with dioxygen to oxidatively cleave the aromatic C-C bond of DBC giving rise to selective extradiol cleavage products. Controlled chemical or electrochemical oxidation of 2, on the other hand, forms an iron(III)-semiquinone radical complex [L(1)Fe(III)(SQ)](PF(6)) (2(ox)-PF(6); SQ = 3,5-di-tert-butylsemiquinonate). The iron(II)-o-aminophenolate complex (3) reacts with dioxygen to afford an iron(III)-o-iminosemiquinonato radical complex [L(1)Fe(III)(ISQ)](ClO(4))(3(ox)-ClO(4); ISQ = 4,6-di-tert-butyl-o-iminobenzosemiquinonato radical) via an iron(III)-o-amidophenolate intermediate species. Structural characterisations of 1, 2, 2(ox) and 3(ox) reveal the presence of a strong iron-carbon bonding interaction in all the complexes. The bond parameters of 2(ox) and 3(ox) clearly establish the radical nature of catecholate- and o-aminophenolate-derived ligand, respectively. The effect of iron-carbon bonding interaction on the dioxygen reactivity of biomimetic iron-catecholate and iron-o-aminophenolate complexes is discussed. SN - 1521-3765 UR - https://www.unboundmedicine.com/medline/citation/22847897/Dioxygen_reactivity_of_biomimetic_iron_catecholate_and_iron_o_aminophenolate_complexes_of_a_tris_2_pyridylthio_methanido_ligand:_aromatic_C_C_bond_cleavage_of_catecholate_versus_o_iminobenzosemiquinonate_radical_formation_ L2 - https://doi.org/10.1002/chem.201200886 DB - PRIME DP - Unbound Medicine ER -
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