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Successive light-induced two electron transfers in a Ru-Fe supramolecular assembly: from Ru-Fe(ii)-OH₂ to Ru-Fe(iv)-oxo.

ABSTRACT: In the present work we describe the synthesis and study of a Ru^II-Fe^II chromophore-catalyst assembly designed to perform the light-induced activation of an iron bound water molecule and subsequent photo-driven oxidation of a substrate. Using a series of spectroscopic techniques, we demonstrate that excitation of the chromophore unit with 450 nm light, in the presence of a sacrificial electron acceptor, triggers a cascade of electron transfers leading to the formation of a high valent iron(iv)-oxo center from an iron(ii)-bound water molecule. The activity of this catalytic center is illustrated by the oxidation of triphenyl phosphine.

SUBMITTER: Herrero C

PROVIDER: S-EPMC5488195 | biostudies-literature | 2015 Apr

REPOSITORIES: biostudies-literature

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Successive light-induced two electron transfers in a Ru-Fe supramolecular assembly: from Ru-Fe(ii)-OH2 to Ru-Fe(iv)-oxo.

Herrero Christian C Quaranta Annamaria A Sircoglou Marie M Sénéchal-David Katell K Baron Aurélie A Marín Irene Mustieles IM Buron Charlotte C Baltaze Jean-Pierre JP Leibl Winfried W Aukauloo Ally A Banse Frédéric F

Chemical science 20150126 4

In the present work we describe the synthesis and study of a RuII-FeII chromophore-catalyst assembly designed to perform the light-induced activation of an iron bound water molecule and subsequent photo-driven oxidation of a substrate. Using a series of spectroscopic techniques, we demonstrate that excitation of the chromophore unit with 450 nm light, in the presence of a sacrificial electron acceptor, triggers a cascade of electron transfers leading to the formation of a h ...[more]

PMID: 28706653

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Project description:High-spin Fe(IV)-oxo species are known to be kinetically competent oxidants in non-heme iron enzymes. The properties of these oxidants are not as well understood as the corresponding intermediate-spin oxidants of heme complexes. The present work gives a detailed characterization of the structurally similar complexes [Fe(IV)H(3)buea(O)](-), [Fe(III)H(3)buea(O)](2-), and [Fe(III)H(3)buea(OH)](-) (H(3)buea = tris[(N'-tert-butylureaylato)-N-ethylene]aminato) using Mössbauer and dual-frequency/dual-mode electron paramagnetic resonance (EPR) spectroscopies. The [Fe(IV)H(3)buea(O)](-) complex has a high-spin (S = 2) configuration imposed by the C(3)-symmetric ligand. The EPR spectra of the [Fe(IV)H(3)buea(O)](-) complex presented here represent the first documented examples of an EPR signal from an Fe(IV)-oxo complex, demonstrating the ability to detect and quantify Fe(IV) species with EPR spectroscopy. Quantitative simulations allowed the determination of the zero-field parameter, D = +4.7 cm(-1), and the species concentration. Density functional theory (DFT) calculations of the zero-field parameter were found to be in agreement with the experimental value and indicated that the major contribution to the D value is from spin-orbit coupling of the ground state with an excited S = 1 electronic configuration at 1.2 eV. (17)O isotope enrichment experiments allowed the determination of the hyperfine constants ((17)O)A(z) = 10 MHz for [Fe(IV)H(3)buea(O)](-) and ((17)O)A(y) = 8 MHz, ((17)O)A(z) = 12 MHz for [Fe(III)H(3)buea(OH)](-). The isotropic hyperfine constant (((17)O)A(iso) = -16.8 MHz) was derived from the experimental value to allow a quantitative determination of the spin polarization (ρ(p) = 0.56) of the oxo p orbitals of the Fe-oxo bond in [Fe(IV)H(3)buea(O)](-). This is the first experimental determination for non-heme complexes and indicates significant covalency in the Fe-oxo bond. High-field Mössbauer spectroscopy gave an (57)Fe A(dip) tensor of (+5.6, +5.3, -10.9) MHz and A(iso) = -25.9 MHz for the [Fe(IV)H(3)buea(O)](-) complex, and the results of DFT calculations were in agreement with the nuclear parameters of the complex.

Dataset Information

Successive light-induced two electron transfers in a Ru-Fe supramolecular assembly: from Ru-Fe(ii)-OH₂ to Ru-Fe(iv)-oxo.

Publications

Successive light-induced two electron transfers in a Ru-Fe supramolecular assembly: from Ru-Fe(ii)-OH<sub>2</sub> to Ru-Fe(iv)-oxo.

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