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Structural, spectroscopic, and electrochemical properties of nonheme Fe(II)-hydroquinonate complexes: synthetic models of hydroquinone dioxygenases.

ABSTRACT: Using the tris(3,5-diphenylpyrazol-1-yl)borate ((Ph2)Tp) supporting ligand, a series of mono- and dinuclear ferrous complexes containing hydroquinonate (HQate) ligands have been prepared and structurally characterized with X-ray crystallography. The monoiron(II) complexes serve as faithful mimics of the substrate-bound form of hydroquinone dioxygenases (HQDOs) - a family of nonheme Fe enzymes that catalyze the oxidative cleavage of 1,4-dihydroxybenzene units. Reflecting the variety of HQDO substrates, the synthetic complexes feature both mono- and bidentate HQate ligands. The bidentate HQates cleanly provide five-coordinate, high-spin Fe(II) complexes with the general formula [Fe((Ph2)Tp)(HL(X))] (1X), where HL(X) is a HQate(1-) ligand substituted at the 2-position with a benzimidazolyl (1A), acetyl (1B and 1C), or methoxy (1D) group. In contrast, the monodentate ligand 2,6-dimethylhydroquinone (H(2)L(F)) exhibited a greater tendency to bridge between two Fe(II) centers, resulting in formation of [Fe(2)((Ph2)Tp)(2)(?-L(F))(MeCN)]·[2F(MeCN)]. However, addition of one equivalent of "free" pyrazole ((Ph2)pz) ligand provided the mononuclear complex, [Fe((Ph2)Tp)(HL(F))((Ph2)pz)]·[1F((Ph2)pz)], which is stabilized by an intramolecular hydrogen bond between the HL(F) and (Ph2)pz donors. Complex 1F((Ph2)pz) represents the first crystallographically-characterized example of a monoiron complex bound to an untethered HQate ligand. The geometric and electronic structures of the Fe/HQate complexes were further probed with spectroscopic (UV-vis absorption, (1)H NMR) and electrochemical methods. Cyclic voltammograms of complexes in the 1X series revealed an Fe-based oxidation between 0 and -300 mV (vs. Fc(+/0)), in addition to irreversible oxidation(s) of the HQate ligand at higher potentials. The one-electron oxidized species (1X(OX)) were examined with UV-vis absorption and electron paramagnetic resonance (EPR) spectroscopies.

SUBMITTER: Baum AE

PROVIDER: S-EPMC3891569 | biostudies-literature | 2012 Oct

REPOSITORIES: biostudies-literature

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Structural, spectroscopic, and electrochemical properties of nonheme Fe(II)-hydroquinonate complexes: synthetic models of hydroquinone dioxygenases.

Baum Amanda E AE Park Heaweon H Wang Denan D Lindeman Sergey V SV Fiedler Adam T AT

Dalton transactions (Cambridge, England : 2003) 20121001 39

Using the tris(3,5-diphenylpyrazol-1-yl)borate ((Ph2)Tp) supporting ligand, a series of mono- and dinuclear ferrous complexes containing hydroquinonate (HQate) ligands have been prepared and structurally characterized with X-ray crystallography. The monoiron(II) complexes serve as faithful mimics of the substrate-bound form of hydroquinone dioxygenases (HQDOs) - a family of nonheme Fe enzymes that catalyze the oxidative cleavage of 1,4-dihydroxybenzene units. Reflecting the variety of HQDO subst ...[more]

PMID: 22930005

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Project description:The oxidative C-C bond cleavage of o-aminophenols by nonheme Fe dioxygenases is a critical step in both human metabolism (the kynurenine pathway) and the microbial degradation of nitroaromatic pollutants. The catalytic cycle of o-aminophenol dioxygenases (APDOs) has been proposed to involve formation of an Fe(II)/O2/iminobenzosemiquinone complex, although the presence of a substrate radical has been called into question by studies of related ring-cleaving dioxygenases. Recently, we reported the first synthesis of an iron(II) complex coordinated to an iminobenzosemiquinone (ISQ) ligand, namely, [Fe((Ph2)Tp)((tBu)ISQ)] (2a; where (Ph2)Tp=hydrotris(3,5-diphenylpyrazol-1-yl)borate and (tBu)ISQ is the radical anion derived from 2-amino-4,6-di-tert-butylphenol). In the current manuscript, density functional theory (DFT) calculations and a wide variety of spectroscopic methods (electronic absorption, Mössbauer, magnetic circular dichroism, and resonance Raman) were employed to obtain detailed electronic-structure descriptions of 2a and its one-electron oxidized derivative [3a](+). In addition, we describe the synthesis and characterization of a parallel series of complexes featuring the neutral supporting ligand tris(4,5-diphenyl-1-methylimidazol-2-yl)phosphine ((Ph2)TIP). The isomer shifts of about 0.97 mm s(-1) obtained through Mössbauer experiments confirm that 2a (and its (Ph2)TIP-based analogue [2b](+)) contain Fe(II) centers, and the presence of an ISQ radical was verified by analysis of the absorption spectra in light of time-dependent DFT calculations. The collective spectroscopic data indicate that one-electron oxidation of the Fe(II)-ISQ complexes yields complexes ([3a](+) and [3b](2+)) with electronic configurations between the Fe(III)-ISQ and Fe(II)-IBQ limits (IBQ=iminobenzoquinone), highlighting the ability of o-amidophenolates to access multiple oxidation states. The implications of these results for the mechanism of APDOs and other ring-cleaving dioxygenases are discussed.

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Structural, spectroscopic, and electrochemical properties of nonheme Fe(II)-hydroquinonate complexes: synthetic models of hydroquinone dioxygenases.

Publications

Structural, spectroscopic, and electrochemical properties of nonheme Fe(II)-hydroquinonate complexes: synthetic models of hydroquinone dioxygenases.

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