Iron(III) complexes of N2O and N3O donor ligands as functional models for catechol dioxygenase enzymes: ether oxygen coordination tunes the regioselectivity and reactivity

Sundaravel, Karuppasamy; Suresh, Eringathodi; Saminathan, Kolandaivelu; Palaniandavar, Mallayan

doi:10.1039/c0dt01598a

Cited by 24 publications

(12 citation statements)

References 84 publications

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“…1.936 Å) than those to the nitrogen atoms (av. 2.016 Å), which are in agreement with the literature values . The bond angles O(1)‐Fe(1)‐N(1), O(2)‐Fe(1)‐N(2) and O(3)‐Fe(1)‐O(4) are all close to 180° [170.298, 166.709 and 173.339°, respectively].…”

Section: Resultssupporting

confidence: 89%

“…2.304(2) Å]. Comparable Fe‐Cl bond lengths have been found in similar octahedral iron(III) complexes reported in the literature …”

Section: Resultssupporting

confidence: 74%

“…Whereas the square base of the octahedral geometry around the Fe(1) center is defined by the N1, N2, O1 and Cl8 atoms, the axial positions are occupied by the Cl2 and Cl12 atoms. The Fe−N and Fe−O bond lengths around the iron(III) center are comparable to the bond lengths observed in similar octahedral iron(III) complexes . In complex 1 , the average axial bond length is greater than the average equatorial bond length [2.401 Å vs .…”

Section: Resultssupporting

confidence: 64%

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Investigating the Coordination/Binding Events of Biologically Relevant Monosaccharides with New Mononuclear Iron(III) and Zinc(II) Complexes in Aqueous Solution

et al. 2017

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New water-soluble mononuclear iron(III) and zinc(II) complexes, (Me 4 N) 4 [Fe 2 OCl 6 ][Fe(pbal)Cl 3 ] 2 (1), (Me 4 N)[Fe(pbal)(NO 3 ) 3 ] (2) and (Me 4 N)[Zn(pbal)Cl 2 ] (3)(Hpbal = N-(2-pyridylmethyl)-b-alanine) have been synthesized and fully characterized. The interactions of the complexes with biologically relevant monosaccharides, such as D-glucose, D-xylose and D-mannose have been studied by UV-Vis, 13 C NMR and ESI-MS techniques in alkaline aqueous solution. All the monosaccharides bind to metal complexes in 1:1 molar ratio. Binding-induced gradual increase in the absorption intensities of 1 and 2 has been observed in the UV-Vis spectra, with a significant blue shift of absorption maxima of the complexes upon increasing the concentration of monosaccharides. The binding ability and binding mode of these monosaccharides with 3 are identified by their characteristic coordination-induced shift (CIS) values for carbon atoms C1 and C2 in the 13 C NMR spectra. The ESI-MS for the complexes under the same experimental conditions but in the presence of one mol equiv. of the applied monosaccharides indicate the formation of complex/monosaccharide-bound associations in solution.

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Section: Resultssupporting

confidence: 89%

“…2.304(2) Å]. Comparable Fe‐Cl bond lengths have been found in similar octahedral iron(III) complexes reported in the literature …”

Section: Resultssupporting

confidence: 74%

Section: Resultssupporting

confidence: 64%

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Investigating the Coordination/Binding Events of Biologically Relevant Monosaccharides with New Mononuclear Iron(III) and Zinc(II) Complexes in Aqueous Solution

et al. 2017

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“…Complexes with L62 or L65 gave a higher percentage of the extradiol products, while for the complex with L63, more intradiol products were formed. The obtained results indicate that the oxygen of the ether group significantly accelerates the reaction [64].…”

Section: Tridentate Ligandsmentioning

confidence: 73%

“…However, the comparison showed that the complexes with tripodal L62-L65 ligands gave the reaction rates more than 10 times higher. The presence of substituents in the ligand rings, their nature, and steric effects significantly affect the acidity of iron (III), which influenced the selectivity of the cleavage reaction [64].…”

Section: Tridentate Ligandsmentioning

confidence: 99%

Biological Inspirations: Iron Complexes Mimicking the Catechol Dioxygenases

et al. 2021

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Within the broad group of Fe non-heme oxidases, our attention was focused on the catechol 1,2- and 2,3-dioxygenases, which catalyze the oxidative cleavage of aromatic rings. A large group of Fe complexes with N/O ligands, ranging from N3 to N2O2S, was developed to mimic the activity of these enzymes. The Fe complexes discussed in this work can mimic the intradiol/extradiol catechol dioxygenase reaction mechanism. Electronic effects of the substituents in the ligand affect the Lewis acidity of the Fe center, increasing the ability to activate dioxygen and enhancing the catalytic activity of the discussed biomimetic complexes. The ligand architecture, the geometric isomers of the complexes, and the substituent steric effects significantly affect the ability to bind the substrate in a monodentate and bidentate manner. The substrate binding mode determines the preferred mechanism and, consequently, the main conversion products. The preferred mechanism of action can also be affected by the solvents and their ability to form the stable complexes with the Fe center. The electrostatic interactions of micellar media, similar to SDS, also control the intradiol/extradiol mechanisms of the catechol conversion by discussed biomimetics.

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Ligand Taxonomy for Bioinorganic Modeling of Dioxygen‐Activating Non‐Heme Iron Enzymes

Park

Lee

2020

Chemistry A European J

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Novel functions emerge from novel structures. To develop efficient catalytic systems for challenging chemical transformations, chemists often seek inspirations from enzymatic catalysis. A large number of iron complexes supported by nitrogen‐rich multidentate ligands have thus been developed to mimic oxo‐transfer reactivity of dioxygen‐activating metalloenzymes. Such efforts have significantly advanced our understanding of the reaction mechanisms by trapping key intermediates and elucidating their geometric and electronic properties. Critical to the success of this biomimetic approach is the design and synthesis of elaborate ligand systems to balance the thermodynamic stability, structural adaptability, and chemical reactivity. In this Concept article, representative design strategies for biomimetic atom‐transfer chemistry are discussed from the perspectives of “ligand builders”. Emphasis is placed on how the primary coordination sphere is constructed, and how it can be elaborated further by rational design for desired functions.

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Iron(III) complexes of N2O and N3O donor ligands as functional models for catechol dioxygenase enzymes: ether oxygen coordination tunes the regioselectivity and reactivity

Cited by 24 publications

References 84 publications

Investigating the Coordination/Binding Events of Biologically Relevant Monosaccharides with New Mononuclear Iron(III) and Zinc(II) Complexes in Aqueous Solution

Investigating the Coordination/Binding Events of Biologically Relevant Monosaccharides with New Mononuclear Iron(III) and Zinc(II) Complexes in Aqueous Solution

Biological Inspirations: Iron Complexes Mimicking the Catechol Dioxygenases

Ligand Taxonomy for Bioinorganic Modeling of Dioxygen‐Activating Non‐Heme Iron Enzymes

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