2:2 Fe(III):ligand and "adamantane core" 4:2 Fe(III):ligand (hydr)oxo complexes of an acyclic ditopic ligand

A bis-hydroxo-bridged diiron(III) complex and a bis-mu-oxo-bis-mu-hydroxo-bridged tetrairon(III) complex are isolated from the reaction of 2,6-bis((N,N'-bis-(2-picolyl)amino)methyl)-4-tert-butylphenol (Hbpbp) with iron perchlorate in acidic and neutral solutions respectively. The X-ray structure of the dinuclear complex [{(Hbpbp)Fe([mu-OH)}(2)](ClO(4))(4).2C(3)H(6)O (1.2C3H6O) shows that only one of the metal-binding cavities of each ligand is occupied by an iron(III) atom and two [Fe(Hbpbp)]3+ units are linked together by two hydroxo bridging groups to form a [Fe(III)-(mu-OH)](2) rhomb structure with Fe...Fe = 3.109(1)A. The non-coordinated tertiary amine of Hbpbp is protonated. Magnetic susceptibility measurements show a well-behaved weak antiferromagnetic coupling between the two Fe(III) atoms, J= -8 cm(-1). The tetranuclear complex [(bpbp)(2)Fe(4)(mu-O)(2)(mu-OH)(2)](ClO(4))(4)(2) was isolated as two different solvates .4CH(3)OH and .6H(2)O with markedly different crystal morphologies at pH ca. 6. Complex .4CH(3)OH forms red cubic crystals and .6H(2)O forms green crystalline platelets. The Fe(4)O(6) core of shows an adamantane-like structure: The six bridging oxygen atoms are provided by the two phenolato groups of the two bpbp(-) ligands, two bridging oxo groups and two bridging hydroxo groups. The hydroxo and oxo ligands could be distinguished on the basis of Fe-O bond lengths of the two different octahedral iron sites: Fe-mu-OH, 1.953(5), 2.013(5)A and Fe-mu-O, 1.803(5), 1.802(5)A. The difference in ligand environment is too small for allowing Mossbauer spectroscopy to distinguish between the two crystallographically independent Fe sites. The best fit to the magnetic susceptibility of .4CH(3)OH was achieved by using three coupling constants J(Fe-OPh-Fe)= 2.6 cm(-1), J(Fe-OH-Fe)=-0.9 cm(-1), J(Fe-O-Fe)=-101 cm(-1) and iron(III) single ion ZFS (|D|= 0.15 cm(-1)).     

Toward identification of the compound I reactive intermediate in cytochrome P450 chemistry: a QM/MM study of its EPR and Mössbauer parameters

Quantum mechanical/molecular mechanical (QM/MM) methods have been used in conjunction with density functional theory (DFT) and correlated ab initio methods to predict the electron paramagnetic resonance (EPR) and Mossbauer (MB) properties of Compound I in P450(cam). For calibration purposes, a small Fe(IV)-oxo complex [Fe(O)(NH(3))(4)(H(2)O)](2+) was studied. The (3)A(2) and (5)A(1) states (in C(4)(v)() symmetry) are found to be within 0.1-0.2 eV. The large zero-field splitting (ZFS) of the (FeO)(2+) unit in the (3)A(2) state arises from spin-orbit coupling with the low-lying quintet and singlet states. The intrinsic g-anisotropy is very small. The spectroscopic properties of the model complex [Fe(O)(TMC)(CH(3)CN)](2+) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) are well reproduced by theory. In the model complexes [Fe(O)(TMP)(X)](+) (TMP = tetramesitylporphyrin, X = nothing or H(2)O) the computations again account for the observed spectroscopic properties and predict that the coupling of the (5)A(1) state of the (FeO)(2+) unit to the porphyrin radical leads to a low-lying sextet/quartet manifold approximately 12 kcal/mol above the quartet ground state. The calculations on cytochrome P450(cam), with and without the simulation of the protein environment by point charges, predict a small antiferromagnetic coupling (J approximately -13 to -16 cm(-)(1); H(HDvV) = - 2JS(A)S(B)) and a large ZFS > 15 cm(-)(1) (with E/D approximately 1/3) which will compete with the exchange coupling. This leads to three Kramers doublets of mixed multiplicity which are all populated at room temperature and may therefore contribute to the observed reactivity. The MB and ligand hyperfine couplings ((14)N, (1)H) are fairly sensitive to the protein environment which controls the spin density distribution between the porphyrin ring and the axial cysteinate ligand.     

High-valent diiron species generated from N-bridged diiron phthalocyanine and H(2)O(2)

N-bridged diiron tetra-tert-butylphthalocyanine activates H(2)O(2) to form anionic hydroperoxo complex [(Pc)Fe(IV)=N-Fe(III)(Pc)-OOH](-) prone to heterolytic cleavage of O-O bond with the release of OH(-) and formation of neutral diiron oxo phthalocyanine cation radical complex, PcFe(IV)=N-Fe(IV)(Pc(+)˙)=O. ESI-MS data showed stability of the Fe-N-Fe binuclear structure upon formation of this species, capable of oxidizing methane and benzene via O-atom transfer. The slow formation kinetics and the high reactivity preclude direct detection of this oxo complex by low temperature UV-vis spectroscopy. However, strong oxidizing properties and the results of EPR study support the formation of PcFe(IV)=N-Fe(IV)(Pc(+)˙)=O. Addition of H(2)O(2) at -80 °C led to the disappearance of iron EPR signal and to the appearance of the narrow signal at g = 2.001 consistent with the transient formation of PcFe(IV)=N-Fe(IV)(Pc(+)˙)=O. In the course of this study, another high valent diiron species was prepared in the solid state with 70% yield. The M?ssbauer spectrum shows two quadrupole doublets with δ(1) = -0.14 mm s(-1), ΔE(Q1) = 1.57 mm s(-1) and δ(2) = -0.10 mm s(-1), ΔE(Q2) = 2.03 mm s(-1), respectively. The negative δ values are consistent with formation of Fe(iv) states. Fe K-edge EXAFS spectroscopy reveals conservation of the diiron Fe-N-Fe core. In XANES, an intense 1s → 3d pre-edge feature at 7114.4 eV suggests formation of Fe(iv) species and attaching of one oxygen atom per two Fe atoms at the 1.90 ? distance. On the basis of M?ssbauer, EPR, EXAFS and XANES data this species was tentatively assigned as (Pc)Fe(IV)=N-Fe(IV)(Pc)-OH which could be formed from PcFe(IV)=N-Fe(IV)(Pc(+)˙)=O by hydrogen atom abstraction from a solvent molecule. Thus, despite unfavourable kinetics, we succeeded in the preparation of the first dirion(iv) phthalocyanine complex with oxygen ligand, generated in the (Pc)Fe(IV)=N-Fe(III)(Pc) - H(2)O(2) system capable of oxidizing methane.     

Mixed-valent [FeIV(mu-O)(mu-carboxylato)2FeIII]3+ core

The symmetrically ligated complexes 1, 2, and 3 with a (mu-oxo)bis(mu-acetato)diferric core can be one-electron oxidized electrochemically or chemically with aminyl radical cations [*NR3][SbCl6] in acetonitrile yielding complexes which contain the mixed-valent [(mu-oxo)bis(mu-acetato)iron(IV)iron(III)]3+ core: [([9]aneN3)(2FeIII2)(mu-O)(mu-CH3CO2)2](ClO4)2 (1(ClO4)2), [(Me3[9]aneN3)(2FeIII2)(mu-O)(mu-CH3CO2)2](PF6)2 (2(PF6)(2)), and [(tpb)(2FeIII2)(mu-O)(mu-CH3CO2)2] (3) where ([9]aneN3) is the neutral triamine 1,4,7-triazacyclononane and (Me3[9]aneN3) is its tris-N-methylated derivative, and (tpb)(-) is the monoanion trispyrazolylborate. The asymmetrically ligated complex [(Me3[9]aneN3)FeIII(mu-O)(mu-CH3CO2)2FeIII(tpb)](PF6) (4(PF6)) and its one-electron oxidized form [4ox]2+ have also been prepared. Finally, the known heterodinuclear species [(Me3[9]aneN3)CrIII(mu-O)(mu-CH3CO2)2Fe([9]aneN3)](PF6)2 (5(PF6)(2)) can also be one-electron oxidized yielding [5ox]3+ containing an iron(IV) ion. The structure of 4(PF6).0.5CH3CN.0.25(C2H5)2O has been determined by X-ray crystallography and that of [5ox]2+ by Fe K-edge EXAFS-spectroscopy (Fe(IV)-O(oxo): 1.69(1) A; Fe(IV)-O(carboxylato) 1.93(3) A, Fe(IV)-N 2.00(2) A) contrasting the data for 5 (Fe(III)-O(oxo) 1.80 A; Fe(III)-O(carboxylato) 2.05 A, Fe-N 2.20 A). [5ox]2+ has an St = 1/2 ground state whereas all complexes containing the mixed-valent [FeIV(mu-O)(mu-CH3CO2)2FeIII]3+ core have an St = 3/2 ground state. M?ssbauer spectra of the oxidized forms of complexes clearly show the presence of low spin FeIV ions (isomer shift approximately 0.02 mm s(-1), quadrupole splitting approximately 1.4 mm s(-1) at 80 K), whereas the high spin FeIII ion exhibits delta approximately 0.46 mm s(-1) and DeltaE(Q) approximately 0.5 mm s(-1). M?ssbauer, EPR spectral and structural parameters have been calculated by density functional theoretical methods at the BP86 and B3LYP levels. The exchange coupling constant, J, for diiron complexes with the mixed-valent FeIV-FeIII core (H = -2J S1.S2; S(1) = 5/2; S2 = 1) has been calculated to be -88 cm(-1) (intramolecular antiferromagnetic coupling) and for the reduced diferric form of -75 cm(-1) in reasonable agreement with experiment (J = -120 cm(-1)).     

X-ray absorption spectroscopy and density functional theory studies of [(H3buea)FeIII-X]n- (X = S2-, O2-, OH-): comparison of bonding and hydrogen bonding in oxo and sulfido complexes

Iron L-edge, iron K-edge, and sulfur K-edge X-ray absorption spectroscopy was performed on a series of compounds [Fe(III)H(3)buea(X)](n-) (X = S(2-), O(2-), OH(-)). The experimentally determined electronic structures were used to correlate to density functional theory calculations. Calculations supported by the data were then used to compare the metal-ligand bonding and to evaluate the effects of H-bonding in Fe(III)(-)O vs Fe(III)(-)S complexes. It was found that the Fe(III)(-)O bond, while less covalent, is stronger than the Fe(III)(-)S bond. This dominantly reflects the larger ionic contribution to the Fe(III)(-)O bond. The H-bonding energy (for three H-bonds) was estimated to be -25 kcal/mol for the oxo as compared to -12 kcal/mol for the sulfide ligand. This difference is attributed to the larger charge density on the oxo ligand resulting from the lower covalency of the Fe-O bond. These results were extended to consider an Fe(IV)(-)O complex with the same ligand environment. It was found that hydrogen bonding to Fe(IV)(-)O is less energetically favorable than that to Fe(III)(-)O, which reflects the highly covalent nature of the Fe(IV)(-)O bond.     

Spectroscopic, magnetochemical, and crystallographic study of cesium iron phosphate hexahydrate: characterization of the electronic structure of the iron(II) hexa-aqua cation in a quasicubic environment

Spectroscopic, magnetochemical, and crystallographic data are presented for CsFe(H2O)6PO4, a member of a little-known isomorphous series of salts that facilitates the study of hexa-aqua ions in a quasicubic environment. Above 120 K, the deviations from cubic symmetry are minimal, as shown by the first example of an iron(II) M?ssbauer spectrum that exhibits no measurable quadrupole splitting. Two crystallographically distinct [Fe(OH2)6]2+ complexes are identified from inelastic neutron-scattering (INS) experiments conducted between 2 and 15 K. The data are modeled with the ligand-field Hamiltonian, H = lambdaL? + betaB(kL + 2?) + Delta(tet){Lz2 - (1/3)L(L + 1)} + Delta(rhom){Lx2 - Ly2}, operating in the ground-term (5)T(2g) (Oh) basis. An excellent reproduction of INS, M?ssbauer, HF-EPR, and magnetochemical data are obtained in the 2 and 15 K temperature regimes with the following parameters: lambda = -80 cm(-1); k = 0.8; site A Delta(tet) = 183 cm(-1), Delta(rhom)= 19 cm(-1); site B Delta(tet) = 181 cm(-1), Delta(rhom)= 12 cm(-1). The corresponding zero-field-splitting (ZFS) parameters of the conventional S = 2 spin Hamiltonian are as follows: site A D = 12.02 cm(-)(1), E = 2.123 cm(-1); site B D = 12.15 cm(-1), E = 1.37 cm(-1). A theoretical analysis of the variation of the energies of the low-lying states with respect to displacements along selected normal coordinates of the [Fe(OH2)6]2+, shows the zero-field splitting to be extremely sensitive to small structural perturbations of the complex. The expressions derived are discussed in the context of spin-Hamiltonian parameters reported for the [Fe(OH2)6]2+ cation in different crystalline environments.     

An abiotic analogue of the diiron(IV)oxo "diamond core" of soluble methane monooxygenase generated by direct activation of O2 in aqueous Fe(II)/EDTA solutions: thermodynamics and electronic structure

We study the generation of a dinuclear Fe(IV)oxo species, [EDTAH·FeO·OFe·EDTAH](2-), in aqueous solution at room temperature using Density Functional Theory (DFT) and Ab Initio Molecular Dynamics (AIMD). This species has been postulated as an intermediate in the multi-step mechanism of autoxidation of Fe(II) to Fe(III) in the presence of atmospheric O(2) and EDTA ligand in water. We examine the formation of [EDTAH·FeO·OFe·EDTAH](2-) by direct cleavage of O(2), and the effects of solvation on the spin state and O-O cleavage barrier. We also study the reactivity of the resulting dinuclear Fe(IV)oxo system in CH(4) hydroxylation, and its tendency to decompose to mononuclear Fe(IV)oxo species. The presence of the solvent is shown to play a crucial role, determining important changes in all these processes compared to the gas phase. We show that, in water solution, [EDTAH·FeO·OFe·EDTAH](2-) (as well as its precursor [EDTAH·Fe·O(2)·Fe·EDTAH](2-)) exists as stable species in a S = 4 ground spin state when hydrogen-bonded to a single water molecule. Its structure comprises two facing Fe(IV)oxo groups, in an arrangement similar to the one evinced for the active centre of intermediate Q of soluble Methane Monooxygenase (sMMO). The inclusion of the water molecule in the complex decreases the overall symmetry of the system, and brings about important changes in the energy and spatial distribution of orbitals of the Fe(IV)oxo groups relative to the gas phase. In particular, the virtual 3σ* orbital of one of the Fe(IV)oxo groups experiences much reduced repulsive orbital interactions from ligand orbitals, and its consequent stabilisation dramatically enhances the electrophilic character of the complex, compared to the symmetrical non-hydrated species, and its ability to act as an acceptor of a H atom from the CH(4) substrate. The computed free energy barrier for H abstraction is 28.2 kJ mol(-1) (at the BLYP level of DFT), considerably below the gas phase value for monomeric [FeO·EDTAH](-), and much below the solution value for the prototype hydrated ferryl ion [FeO(H(2)O)(5)](2+).     

Determination by high-frequency and -field EPR of zero-field splitting in iron(IV) oxo complexes: implications for intermediates in nonheme iron enzymes

[Fe(IV)O](2+) species have been implicated as the active form of many nonheme iron enzymes. The electronic structures of iron(IV) oxo complexes are thus of great interest. High-frequency and -field electron paramagnetic resonance is employed to determine accurately the spin Hamiltonian parameters of two stable complexes that contain the FeO unit: [FeO(TMC)(CH 3CN)](CF 3SO 3) 2, where TMC = tetramethylcyclam and [FeO(N4py)](CF 3SO 3) 2, where N4Py = bis(2-pyridylmethyl)bis(2-pyridyl)methylamine. Both complexes exhibit zero-field splittings that are positive, almost perfectly axial, and of very large magnitude: D = +26.95(5) and +22.05(5) cm (-1), respectively. These definitive experimental values can serve as the basis for further computational studies to unravel the electronic structures of such complexes.     

FTIR spectra and normal-mode analysis of a tetranuclear manganese adamantane-like complex in two electrochemically prepared oxidation states: relevance to the oxygen-evolving complex of photosystem II

The IR spectra and normal-mode analysis of the adamantane-like compound [Mn(4)O(6)(bpea)(4)](n+) (bpea = N,N-bis(2-pyridylmethyl)ethylamine) in two oxidation states, Mn(IV)(4) and Mn(III)Mn(IV)(3), that are relevant to the oxygen-evolving complex of photosystem II are presented. Mn-O vibrational modes are identified with isotopic exchange, (16)O-->(18)O, of the mono-micro-oxo bridging atoms in the complex. IR spectra of the Mn(III)Mn(IV)(3) species are obtained by electrochemical reduction of the Mn(IV)(4) species using a spectroelectrochemical cell, based on attenuated total reflection [Visser, H.; et al. Anal. Chem. 2001, 73, 4374-4378]. A novel method of subtraction is used to reduce background contributions from solvent and ligand modes, and the difference and double-difference spectra are used in identifying Mn-O bridging modes that are sensitive to oxidation state change. Two strong IR bands are observed for the Mn(IV)(4) species at 745 and 707 cm(-1), and a weaker band is observed at 510 cm(-1). Upon reduction, the Mn(III)Mn(IV)(3) species exhibits two strong IR bands at 745 and 680 cm(-1), and several weaker bands are observed in the 510-425 cm(-1) range. A normal-mode analysis is performed to assign all the relevant bridging modes in the oxidized Mn(IV)(4) and reduced Mn(III)Mn(IV)(3) species. The calculated force constants for the Mn(IV)(4) species are f(r)(IV)= 3.15 mdyn/A, f(rOr) = 0.55 mdyn/A, and f(rMnr) = 0.20 mdyn/A. The force constants for the Mn(III)Mn(IV)(3) species are f(r)(IV)= 3.10 mdyn/A, f(r)(III)= 2.45 mdyn/A, f(rOr) = 0.40 mdyn/A, and f(rMnr) = 0.15 mdyn/A. This study provides insights for the identification of Mn-O modes in the IR spectra of the photosynthetic oxygen-evolving complex during its catalytic cycle.     

High-valent nonheme iron. Two distinct iron(IV) species derived from a common iron(II) precursor

The reaction of [Fe(II)(beta-BPMCN)(OTf)2] (1, BPMCN = N,N'-bis(2-pyridylmethyl)-N,N'-dimethyl-trans-1,2-diaminocyclohexane) with tBuOOH at low-temperature yields alkylperoxoiron(III) intermediates 2 in CH2Cl2 and 2-NCMe in CH3CN. At -45 degrees C and above, 2-NCMe converts to a pale green species 3 (lambda(max) = 753 nm, epsilon = 280 M(-1) cm(-1)) in 90% yield, identified as [Fe(IV)(O)(BPMCN)(NCCH3)]2+ by comparison to other nonheme [Fe(IV)(O)(L)]2+ complexes. Below -55 degrees C in CH2Cl2, 2 decays instead to form deep turquoise 4 (lambda(max) = 656, 845 nm; epsilon = 4000, 3600 M(-1) cm(-1)), formulated to be an unprecedented alkylperoxoiron(IV) complex [Fe(IV)(BPMCN)(OH)(OOtBu)]2+ on the basis of M?ssbauer, EXAFS, resonance Raman, NMR, and mass spectral evidence. The reactivity of 1 with tBuOOH in the two solvents reveals an unexpectedly rich iron(IV) chemistry that can be supported by the BPMCN ligand.     

Studies of a linear single-molecule magnet

Reaction of the dinuclear complex [Mn2O2(bpy)4](ClO4)3 with H3cht (cis,cis-l,3,5-cyclohexanetriol) in MeCN produces the complex [Mn3(Hcht)2(bpy)4](ClO4)3.Et2O.2MeCN (1.Et2O.2MeCN). Dc magnetic susceptibility measurements reveal the existence of weak ferromagnetic exchange between the three Mn ions, leading to a spin ground state of S = 7, with D = -0.23 cm(-1). W-Band (94 GHz) EPR measurements on restrained powdered crystalline samples confirm the S = 7 ground state and determine the ground state zero-field splitting (ZFS) parameters of D = -0.14 cm(-1) and B4(0)= +1.5 x 10(-5) cm(-1). The apparent 4th order behaviour is due to a breakdown of the strong exchange limit approximation (J approximately d, the single-ion ZFS). Single crystal dc relaxation decay and hysteresis loop measurements reveal the molecule to have an appreciable energy barrier to magnetization relaxation, displaying low temperature sweep rate and temperature-dependent hysteresis loops. Density functional studies confirm the ferromagnetic exchange coupling between the Mn ions.     

Single-ion versus dipolar origin of the magnetic anisotropy in iron(III)-oxo clusters: a case study

A multitechnique approach has allowed the first experimental determination of single-ion anisotropies in a large iron(III)-oxo cluster, namely [NaFe6(OCH3)12(pmdbm)6ClO4 (1) in which Hpmdbm = 1,3-bis(4-methoxyphenyl)-1,3-propanedione. High-frequency EPR (HF-EPR). bulk susceptibility measurements, and high-field cantilever torque magnetometry (HF-CTM) have been applied to iron-doped samples of an isomorphous hexagallium(III) cluster [NaGa6(OCH3)12-(pmdbm)6]ClO4, whose synthesis and X-ray structure are also presented. HF-EPR at 240 GHz and susceptibility data have shown that the iron(III) ions have a hard-axis type anisotropy with DFe = 0.43(1) cm(-1) and EFe = 0.066(3) cm(-1) in the zero-field splitting (ZFS) Hamiltonian H = DFe[S2(z) - S(S + 1)/3] + Fe[S2(x) - S2(y)]. HF-CTM at 0.4 K has then been used to establish the orientation of the ZFS tensors with respect to the unique molecular axis of the cluster, Z. The hard magnetic axes of the iron(III) ions are found to be almost perpendicular to Z, so that the anisotropic components projected onto Z are negative, DFe(ZZ)= -0.164(4) cm(-1). Due to the dominant antiferromagnetic coupling, a negative DFe(ZZ) value determines a hard-axis molecular anisotropy in 1, as experimentally observed. By adding point-dipolar interactions between iron(III) spins, the calculated ZFS parameter of the triplet state, D1 = 4.70(9) cm(-1), is in excellent agreement with that determined by inelastic neutron scattering experiments at 2 K, D1 = 4.57(2) cm(-1). Iron-doped samples of a structurally related compound, the dimer [Ga2(OCH3)2(dbm)4] (Hdbm = dibenzoylmethane), have also been investigated by HF-EPR at 525 GHz. The single-ion anisotropy is of the hard-axis type as well, but the DFe parameter is significantly larger [DFe = 0.770(3) cm(-1). EFe = 0.090(3) cm(-1)]. We conclude that, although the ZFS tensors depend very unpredictably on the coordination environment of the metal ions, single-ion terms can contribute significantly to the magnetic anisotropy of iron(III)-oxo clusters, which are currently investigated as single-molecule magnets.     

Synthesis and Crystal Structure of Compound [Fe(Phen)_3][(μ-oxo)Fe_2Cl_6]DMF

1 INTRODUCTION Recently polynuclear iron (Ⅲ) clusters have attracted considerable attention in bioinorganic chemistry due to their presence in the protein ferritin and the related materical hemosiderin[1, 2]. The binuclear oxo-bridge non-haem iron com- plexes (containing the FeⅢOFeⅢ unit) which provide models for the diiron site in the protein involved in the storage (haemrythrin) and on the reductive activation (methanemonoxygenas， ribonclectidereductas) of dioxygen[3,4]. Also, wel…     

Electron paramagnetic resonance and Mössbauer spectroscopy and density functional theory analysis of a high-spin Fe(IV)-oxo complex

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 M?ssbauer 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 M?ssbauer 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.     

(TAML)FeIV O complex in aqueous solution: synthesis and spectroscopic and computational characterization

Recently, we reported the characterization of the S = (1)/ 2 complex [Fe (V)(O)B*] (-), where B* belongs to a family of tetraamido macrocyclic ligands (TAMLs) whose iron complexes activate peroxides for environmentally useful applications. The corresponding one-electron reduced species, [Fe (IV)(O)B*] (2-) ( 2), has now been prepared in >95% yield in aqueous solution at pH > 12 by oxidation of [Fe (III)(H 2O)B*] (-) ( 1), with tert-butyl hydroperoxide. At room temperature, the monomeric species 2 is in a reversible, pH-dependent equilibrium with dimeric species [B*Fe (IV)-O-Fe (IV)B*] (2-) ( 3), with a p K a near 10. In zero field, the M?ssbauer spectrum of 2 exhibits a quadrupole doublet with Delta E Q = 3.95(3) mm/s and delta = -0.19(2) mm/s, parameters consistent with a S = 1 Fe (IV) state. Studies in applied magnetic fields yielded the zero-field splitting parameter D = 24(3) cm (-1) together with the magnetic hyperfine tensor A/ g nbeta n = (-27, -27, +2) T. Fe K-edge EXAFS analysis of 2 shows a scatterer at 1.69 (2) A, a distance consistent with a Fe (IV)O bond. DFT calculations for [Fe (IV)(O)B*] (2-) reproduce the experimental data quite well. Further significant improvement was achieved by introducing hydrogen bonding of the axial oxygen with two solvent-water molecules. It is shown, using DFT, that the (57)Fe hyperfine parameters of complex 2 give evidence for strong electron donation from B* to iron.     

Oxo iron(IV) as an oxidative active intermediate of p-chlorophenol in the Fenton reaction: a DFT study

Debate continues over which active species plays the role of oxidative agent during the Fenton reaction-the HO˙ radical or oxo iron [Fe(IV)O](2+). In this context, the present study investigates the oxidation of p-chlorophenol by [Fe(IV)O(H(2)O)(5)](2+) using DFT calculations, within gas-phase and micro-solvated models, in order to explore the possible role of oxo iron as a reactant. The results show that the chlorine atom substitution of p-chlorophenol by oxo iron is a highly stabilising step (ΔH = -83 kcal mol(-1)) with a free energy barrier of 5.8 kcal mol(-1) in the micro-solvated model. This illustrates the high oxidising power of the [Fe(IV)O(H(2)O)(5)](2+) complex. On the other hand, the breaking of the Fe-O bond, leading to the formation of hydroquinone, is observed to be the rate-determining step of the reaction. The rather large free energy barrier corresponding to this bond cleavage amounts to 10.2 and 9.3 kcal mol(-1) in the gas-phase and micro-solvated models, respectively. Elsewhere, the lifetime of the HO˙ radical has previously been shown to be extremely small. These facts, combined with observations of oxo iron under certain experimental conditions, suggest that oxo iron is a highly plausible oxidative species of the reaction. In addition, a trigonal bipyramidal iron complex, coordinated either by hydroxyl groups and/or by water molecules, has been found in all described mechanisms. This structure appears to be a stable intermediate; and to our knowledge, it has not been characterised by previous studies.     

Molecular and electronic structures of dinuclear iron complexes incorporating strongly electron-donating ligands: implications for the generation of the one- and two-electron oxidized forms

The ligands (L(t-Bu(2)))(2-), (L(Me(2)))(2-), and (L(Cl(2)))(2-) have been employed for the synthesis of the dinuclear Fe(III) complexes [L(t-Bu(2))Fe(μ-O)FeL(t-Bu(2))], [L(Me(2))Fe(μ-O)FeL(Me(2))], and [L(Cl(2))Fe(μ-O)FeL(Cl(2))]. The strongly electron-donating groups (tert-amines and phenolates) were chosen to increase the electron density at the coordinated ferric ions and thus to facilitate the oxidation of the complexes, with the possibility of fine-tuning the electronic structures by variation of the remote substituents. Molecular structures established in the solid (by single-crystal X-ray diffraction) and in solution (by X-ray absorption spectroscopy) show that the Fe ions are five-coordinate in a square-pyramidal coordination environment with the ligand adopting a trans-conformation. Spectroscopic and magnetic characterization establishes the highly covalent nature of the Fe(III)-O(oxo) and Fe(III)-O(Ph) bonds. The variations in the donor capabilities of the phenolates (due to changes in the remote substituents) are compensated for by a flexible electron donation of the Fe(III)-O(oxo) bonding. Spectroelectrochemical characterization demonstrates that [L(t-Bu(2))Fe(μ-O)FeL(t-Bu(2))] can be oxidized reversibly at +0.27 and +0.44 V versus Fc(+)/Fc, whereas [L(Me(2))Fe(μ-O)FeL(Me(2))] and [L(Cl(2))Fe(μ-O)FeL(Cl(2))] exhibit irreversible oxidations at +0.29 and +0.87 V versus Fc(+)/Fc, respectively. UV-vis, electron paramagnetic resonance (EPR), X-ray absorption spectroscopy (XAS), and Mo?ssbauer spectroscopy show that the successive oxidations of [L(t-Bu(2))Fe(μ-O)FeL(t-Bu(2))] are ligand-centered leading to the monophenoxyl radical complex [(?)L(t-Bu(2))Fe(III)(μ-O)Fe(III)L(t-Bu(2))](+) (with the oxidation primarily localized on one-half of the molecule) and the diphenoxyl radical complex [(?)L(t-Bu(2))Fe(III)(μ-O)Fe(III?)L(t-Bu(2))](2+). Both products are unstable in solution and decay by cleavage of an Fe(III)-O(oxo) bond. The two-electron oxidized species is more stable because of two equally strong Fe(III)-O(oxo) bonds, whereas in the singly oxidized species the Fe(III)-O(oxo) bond of the non-oxidized half is weakened. The decay of the monocation results in the formation of [L(t-Bu(2))Fe(III)](+) and [L(t-Bu(2))Fe(IV)=O], while the decay of the dication yields [(?)L(t-Bu(2))Fe(III)](2+) and [L(t-Bu(2))Fe(IV)=O]. Follow-up reactions of the oxidized fragments with the counteranion of the oxidant, [SbCl(6)](-), leads to the formation of [Fe(III)Cl(4)](-).     

Two new terpyridine dimanganese complexes: a manganese(III,III) complex with a single unsupported oxo bridge and a manganese(III,IV) complex with a dioxo bridge. Synthesis, structure, and redox properties

Two new terpyridine dimanganese oxo complexes [Mn(2)(III,IV)(mu-O)(2)(terpy)(2)(CF(3)CO(2))(2)](+) (3) and [Mn(2)(III,III)(mu-O)(terpy)(2)(CF(3)CO(2))(4)] (4) (terpy = 2,2':6,2' '-terpyridine) have been synthesized and their X-ray structures determined. In contrast to the corresponding mixed-valent aqua complex [Mn(2)(III,IV)(mu-O)(2)(terpy)(2)(H(2)O)(2)](3+) (1), the two Mn atoms in 3 are not crystallographically equivalent. The neutral binuclear monooxo manganese(III,III) complex 4 exhibits two crystallographic forms having cis and trans configurations. In the cis complex, the two CF(3)CO(2)(-) ligands on each manganese adopt a cis geometry to each other; one CF(3)CO(2)(-) is trans to the oxygen of the oxo bridge while the second is cis. In the trans complex, the two coordinated CF(3)CO(2)(-) have a trans geometry to each other and are cis to the oxo bridge. The electrochemical behavior of 3 in organic medium (CH(3)CN) shows that this complex could be oxidized into its corresponding stable manganese(IV,IV) species while its reduced form manganese(III,III) is very unstable and leads by a disproportionation process to Mn(II) and Mn(IV) complexes. Complex 4 is only stable in the solid state, and it disproportionates spontaneously in CH(3)CN solution into the mixed-valent complex 3 and the mononuclear complex [Mn(II)(terpy)(2)](2+) (2), thereby preventing the observation of its electrochemical behavior.     

Utilization of hydrogen bonds to stabilize M-O(H) units: synthesis and properties of monomeric iron and manganese complexes with terminal oxo and hydroxo ligands

Non-heme iron and manganese species with terminal oxo ligands are proposed to be key intermediates in a variety of biological and synthetic systems; however, the stabilization of these types of complexes has proven difficult because of the tendency to form oxo-bridged complexes. Described herein are the design, isolation, and properties for a series of mononuclear Fe(III) and Mn(III) complexes with terminal oxo or hydroxo ligands. Isolation of the complexes was facilitated by the tripodal ligand tris[(N'-tert-butylureaylato)-N-ethyl]aminato ([H(3)1](3-)), which creates a protective hydrogen bond cavity around the M(III)-O(H) units (M(III) = Fe and Mn). The M(III)-O(H) complexes are prepared by the activation of dioxygen and deprotonation of water. In addition, the M(III)-O(H) complexes can be synthesized using oxygen atom transfer reagents such as N-oxides and hydroxylamines. The [Fe(III)H(3)1(O)](2-) complex also can be made using sulfoxides. These findings support the proposal of a high valent M(IV)-oxo species as an intermediate during dioxygen cleavage. Isotopic labeling studies show that oxo ligands in the [M(III)H(3)1(O)](2-) complexes come directly from the cleavage of dioxygen: for [Fe(III)H(3)1(O)](2-) the nu(Fe-(16)O) = 671 cm(-1), which shifts 26 cm(-1) in [Fe(III)H(3)1((18)O)](2-) (nu(Fe-(18)O) = 645 cm(-1)); a nu(Mn-(16)O) = 700 cm(-1) was observed for [Mn(III)H(3)1((16)O)](2-), which shifts to 672 cm(-1) in the Mn-(18)O isotopomer. X-ray diffraction studies show that the Fe-O distance is 1.813(3) A in [Fe(III)H(3)1(O)](2-), while a longer bond is found in [Fe(III)H(3)1(OH)](-) (Fe-O at 1.926(2) A); a similar trend was found for the Mn(III)-O(H) complexes, where a Mn-O distance of 1.771(5) A is observed for [Mn(III)H(3)1(O)](2-) and 1.873(2) A for [Mn(III)H(3)1(OH)](-). Strong intramolecular hydrogen bonds between the urea NH groups of [H(3)1](3-) and the oxo and oxygen of the hydroxo ligand are observed in all the complexes. These findings, along with density functional theory calculations, indicate that a single sigma-bond exists between the M(III) centers and the oxo ligands, and additional interactions to the oxo ligands arise from intramolecular H-bonds, which illustrates that noncovalent interactions may replace pi-bonds in stabilizing oxometal complexes.     

Hydrogen atom abstraction by a mononuclear ferric hydroxide complex: insights into the reactivity of lipoxygenase

The lipoxygenase mimic [Fe(III)(PY5)(OH)](CF3SO3)2 is synthesized from the reaction of [Fe(II)(PY5)(MeCN)](CF3SO3)2 with iodosobenzene, with low-temperature studies suggesting the possible intermediacy of an Fe(IV) oxo species. The Fe(III)-OH complex is isolated and identified by a combination of solution and solid-state methods, including EPR and IR spectroscopy. [Fe(III)(PY5)(OH)](2+) reacts with weak X-H bonds in a manner consistent with hydrogen-atom abstraction. The composition of this complex allows meaningful comparisons to be made with previously reported Mn(III)-OH and Fe(III)-OMe lipoxygenase mimics. The bond dissociation energy (BDE) of the O-H bond formed upon reduction to [Fe(II)(PY5)(H2O)]2+ is estimated to be 80 kcal mol(-1), 2 kcal mol(-1) lower than that in the structurally analogous [Mn(II)(PY5)(H2O)]2+ complex, supporting the generally accepted idea that Mn(III) is the thermodynamically superior oxidant at parity of coordination sphere. The identity of the metal has a large influence on the entropy of activation for the reaction with 9,10-dihydroanthracene; [Mn(III)(PY5)(OH)]2+ has a 10 eu more negative DeltaS++ value than either [Fe(III)(PY5)(OH)]2+ or [Fe(III)(PY5)(OMe)]2+, presumably because of the increased structural reorganization that occurs upon reduction to [Mn(II)(PY5)(H2O)]2+. The greater enthalpic driving force for the reduction of Mn(III) correlates with [Mn(III)(PY5)(OH)]2+ reacting more quickly than [Fe(III)(PY5)(OH)]2+. Curiously, [Fe(III)(PY5)(OMe)]2+ reacts with substrates only about twice as fast as [Fe(III)(PY5)(OH)]2+, despite a 4 kcal mol(-1) greater enthalpic driving force for the methoxide complex.