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Mossbauer, electron paramagnetic resonance, and density functional theory studies of synthetic S = 1/2 Fe(III)-O-Fe(IV)?O complexes. Superexchange-mediated spin transition at the Fe(IV)?O site.

ABSTRACT: Previously we have characterized two high-valent complexes [LFe(IV)(?-O)(2)Fe(III)L], 1, and [LFe(IV)(O)(?-O)(OH) Fe(IV)L], 4. Addition of hydroxide or fluoride to 1 produces two new complexes, 1-OH and 1-F. Electron paramagnetic resonance (EPR) and Mo?ssbauer studies show that both complexes have an S = 1/2 ground state which results from antiferromagnetic coupling of the spins of a high-spin (S(a) = 5/2) Fe(III) and a high-spin (S(b) = 2) Fe(IV) site. 1-OH can also be obtained by a 1-electron reduction of 4, which has been shown to have an Fe(IV)?O site. Radiolytic reduction of 4 at 77 K yields a Mo?ssbauer spectrum identical to that observed for 1-OH, showing that the latter contains an Fe(IV)?O. Interestingly, the Fe(IV)?O moiety has S(b) = 1 in 4 and S(b) = 2 in 1-OH and 1-F. From the temperature dependence of the S = 1/2 signal we have determined the exchange coupling constant J (? = JS(a)·S(b) convention) to be 90 ± 20 cm(-1) for both 1-OH and 1-F. Broken-symmetry density functional theory (DFT) calculations yield J = 135 cm(-1) for 1-OH and J = 104 cm(-1) for 1-F, in good agreement with the experiments. DFT analysis shows that the S(b) = 1 ? S(b) = 2 transition of the Fe(IV)?O site upon reduction of the Fe(IV)-OH site to high-spin Fe(III) is driven primarily by the strong antiferromagnetic exchange in the (S(a) = 5/2, S(b) = 2) couple.

SUBMITTER: De Hont RF

PROVIDER: S-EPMC2957120 | biostudies-literature | 2010 Sep

REPOSITORIES: biostudies-literature

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Mössbauer, electron paramagnetic resonance, and density functional theory studies of synthetic S = 1/2 Fe(III)-O-Fe(IV)═O complexes. Superexchange-mediated spin transition at the Fe(IV)═O site.

De Hont Raymond F RF Xue Genqiang G Hendrich Michael P MP Que Lawrence L Bominaar Emile L EL Münck Eckard E

Inorganic chemistry 20100901 18

Previously we have characterized two high-valent complexes [LFe(IV)(μ-O)(2)Fe(III)L], 1, and [LFe(IV)(O)(μ-O)(OH) Fe(IV)L], 4. Addition of hydroxide or fluoride to 1 produces two new complexes, 1-OH and 1-F. Electron paramagnetic resonance (EPR) and Mössbauer studies show that both complexes have an S = 1/2 ground state which results from antiferromagnetic coupling of the spins of a high-spin (S(a) = 5/2) Fe(III) and a high-spin (S(b) = 2) Fe(IV) site. 1-OH can also be obtained by a 1-electron r ...[more]

PMID: 20795646

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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.

Project description:The synthesis and crystallographic characterization of a new family of M(mu-CN)Ln complexes are reported. Two structural series have been prepared by reacting in water rare earth nitrates (Ln(III) = La, Pr, Nd, Sm, Eu, Gd, Dy, Ho) with K(3)[M(CN)(6)] (M(III) = Fe, Co) in the presence of hexamethylenetetramine (hmt). The first series consists of six isomorphous heterobinuclear complexes, [(CN)(5)M-CN-Ln(H(2)O)(8)].2hmt ([FeLa] 1, [FePr] 2, [FeNd] 3, [FeSm] 4, [FeEu] 5, [FeGd] 6), while the second series consists of four isostructural ionic complexes, [M(CN)(6)][Ln(H(2)O)(8)].hmt ([FeDy] 7, [FeHo] 8, [CoEu] 9, [CoGd] 10). The hexamethylenetetramine molecules contribute to the stabilization of the crystals by participating in an extended network of hydrogen bond interactions. In both series the aqua ligands are hydrogen bonded to the nitrogen atoms from both the terminal CN(-) groups and the hmt molecules. The [FeGd] complex has been analyzed with (57)Fe Mossbauer spectroscopy and magnetic susceptibility measurements. We have also analyzed the [FeLa] complex, in which the paramagnetic Gd(III) is replaced by diamagnetic La(III), with (57)Fe Mossbauer spectroscopy, electron paramagnetic resonance (EPR), and magnetic susceptibility measurements, to obtain information about the low-spin Fe(III) site that is not accessible in the presence of a paramagnetic ion at the complementary site. For the same reason, the [CoGd] complex, containing diamagnetic Co(III), was studied with EPR and magnetic susceptibility measurements, which confirmed the S = 7/2 spin of Gd(III). Prior knowledge about the paramagnetic sites in [FeGd] allows a detailed analysis of the exchange interactions between them. In particular, the question of whether the exchange interaction in [FeGd] is isotropic or anisotropic has been addressed. Standard variable-temperature magnetic susceptibility measurements provide only the value for a linear combination of J(x), J(y), and J(z) but contain no information about the values of the individual exchange parameters J(x), J(y), and J(z). In contrast, the spin-Hamiltonian analysis of the variable-field, variable-temperature Mossbauer spectra reveals an exquisite sensitivity on the anisotropic exchange parameters. Analysis of these dependencies in conjunction with adopting the g-values obtained for [FeLa], yielded the values J(x) = +0.11 cm(-1), J(y) = +0.33 cm(-1), and J(z) = +1.20 cm(-1) (S(1).J.S(2) convention). The consistency of these results with magnetic susceptibility data is analyzed. The exchange anisotropy is rooted in the spatial anisotropy of the low-spin Fe(III) ion. The condition for anisotropic exchange is the presence of low-lying orbital excited states at the ferric site that (i) effectively interact through spin-orbit coupling with the orbital ground state and (ii) have an exchange parameter with the Gd site with a value different from that for the ground state. Density functional theory (DFT) calculations, without spin-orbit coupling, reveal that the unpaired electron of the t(2g)(5) ground configuration of the Fe(III) ion occupies the xy orbital, that is, the orbital along the plane perpendicular to the Fe...Gd vector. The exchange-coupling constants for this orbital, j(xy), and for the other t(2g) orbitals, j(yz) and j(xz), have been determined using a theoretical model that relates them to the anisotropic exchange parameters and the g-values of Fe(III). The resulting values, j(yz) = -5.7 cm(-1), j(xz) = -4.9 cm(-1), and j(xy) = +0.3 cm(-1) are quite different. The origin of the difference is briefly discussed.

Dataset Information

Mossbauer, electron paramagnetic resonance, and density functional theory studies of synthetic S = 1/2 Fe(III)-O-Fe(IV)?O complexes. Superexchange-mediated spin transition at the Fe(IV)?O site.

Publications

Mössbauer, electron paramagnetic resonance, and density functional theory studies of synthetic S = 1/2 Fe(III)-O-Fe(IV)═O complexes. Superexchange-mediated spin transition at the Fe(IV)═O site.

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