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)).     

Complex formation reaction of the iron(III) hydroxo dimer with periodate ion

The kinetics and mechanism of the ligand substitution reaction between Fe(2)(OH)(2)(4+) and periodate ion has been studied. This process is unique among the reactions of the iron(iii) hydroxo dimer because the initial rate is second-order with respect to Fe(2)(OH)(2)(4+). The formation of a bi- and a tetranuclear complex, Fe(2)(OH)(2)(H(4)IO(6))(3+) and Fe(4)(OH)(4)(H(4)IO(6))(7+), is proposed. Comprehensive fitting of the kinetic data was used to show that the proposed model, which is very similar to earlier models used with other inorganic oxoanions, gives a reasonable interpretation of all observations. It is shown that the lifetime of Fe(2)(OH)(2)(H(4)IO(6))(3+) is relatively long and it can open a pathway to form oligomeric and less soluble products at higher initial concentrations. The speciation of aqueous periodate ion solution was also studied and it is proposed that the tetrahedral form, IO(4)(-), is less dominant over the octahedral form, H(4)IO(6)(-), than previously thought.     

Dinuclear and 1D iron(III) Schiff base complexes bridged by 4-salicylideneamino-1,2,4-triazolate: X-ray structures and magnetic properties

Four new iron(III) complexes were obtained by the reaction of 4-salicylideneamino-1,2,4-triazole (Hsaltrz) and selected dinuclear μ-oxo-bridged iron(III) Schiff base complexes [{FeL(4)}(2)(μ-O)], where L(4) represents a terminal tetradentate dianionic Schiff-base ligand. X-ray structural analysis revealed a novel bridging mode of κN,κO of the saltrz ligand to form dinuclear complexes [{Fe(salen)(μ-saltrz)}(2)]·CH(3)OH (1) (H(2)salen = N,N'-ethylenebis(salicylimine)) and [{Fe(salpn)(μ-saltrz)}(2)] (2) (H(2)salpn = N,N'-1,2-propylenbis(salicylimine)), whereas one-dimensional (1D) zig-zag chains were formed in the case of [{Fe(salch)(μ-saltrz)}·0.5CH(3)OH](n) (3) (H(2)salch = N,N'-cyclohexanebis(salicylimine)) and [Fe(salophen)(μ-saltrz)](n) (4) (H(2)salophen = N,N'-o-phenylenebis(salicylimine)). It was also shown that the rigidity of the terminal ligand L(4) can be considered as the key factor for the molecular dimensionality of the products. The thorough magnetic analysis based on SQUID experiments, including the isotropic exchange and the zero-field splitting of both temperature and field dependent data, was performed for dimeric (1 and 2) and also for polymeric compounds (3 and 4) and revealed weak antiferromagnetic exchange mediated by the saltrz anions with much larger D-parameter (|D|?|J|).     

Multiple-path dissociation mechanism for mono- and dinuclear tris(hydroxamato)iron(III) complexes with dihydroxamic acid ligands in aqueous solution

Linear synthetic dihydroxamic acids ([CH3N(OH)C=O)]2(CH2)n; H2Ln) with short (n = 2) and long (n = 8) hydrocarbon-connecting chains form mono- and dinuclear complexes with Fe(III) in aqueous solution. At conditions where the formation of Fe2(Ln)3 is favored, complexes with each of the two ligand systems undergo [H+]-induced ligand dissociation processes via multiple sequential and parallel paths, some of which are common and some of which are different for the two ligands. The pH jump induced ligand dissociation proceeds in two major stages (I and II) where each stage is shown to be comprised of multiple components (Ix, where x = 1-3 for L2 and L8, and IIy, where y = 1-3 for L2 and y = 1-4 for L8). A reaction scheme consistent with kinetic and independent ESI-MS data is proposed that includes the tris-chelated complexes (coordinated H2O omitted for clarity) (Fe2(Ln)3, Fe2(L2)2(L2H)2, Fe(LnH)3, Fe(L8)(L8H)), bis-chelated complexes (Fe2(Ln)2(2+), Fe(LnH)2+, Fe(L8)+), and monochelated complexes (Fe(LnH)2+). Analysis of kinetic data for ligand dissociation from Fe2(Ln)(LnH)3+ (n = 2, 4, 6, 8) allows us to estimate the dielectric constant at the reactive dinuclear Fe(III) site. The existence of multiple ligand dissociation paths for the dihydroxamic acid complexes of Fe(III) is a feature that distinguishes these systems from their bidentate monohydroxamic acid and hexadentate trihydroxamic acid counterparts and may be a reason for the biosynthesis of dihydroxamic acid siderophores, despite higher environmental molar concentrations necessary to completely chelate Fe(III).     

Monomeric iron(II) hydroxo and iron(III) dihydroxo complexes stabilized by intermolecular hydrogen bonding

Using the multidentate ligand bis(N-methylimidazol-2-yl)-3-methylthiopropanol (L), the mononuclear iron(II) hydroxo and iron(III) dihydroxo complexes [Fe(II)(L)2(OH)](BF4) (1) and [Fe(III)(L)2(OH)2](BF4) (2) have been synthesized and characterized by X-ray diffraction and spectroscopic methods. The X-ray data suggest that the remarkable stability of the Fe-OH bond(s) in both compounds results from intermolecular hydrogen-bonding interactions between the hydroxo ligand(s) and the tertiary hydroxyl of the L ligands, which prevent further intermolecular reactions.     

Proton control of oxidation and spin state in a series of iron tripodal imidazole complexes

Reaction of iron salts with three tripodal imidazole ligands, H(3)(1), H(3)(2), H(3)(3), formed from the condensation of tris(2-aminoethyl)amine (tren) with 3 equiv of an imidazole carboxaldehyde yielded eight new cationic iron(III) and iron(II), [FeH(3)L](3+or2+), and neutral iron(III), FeL, complexes. All complexes were characterized by EA(CHN), IR, UV, M?ssbauer, mass spectral techniques and cyclic voltammetry. Structures of three of the complexes, Fe(2).3H(2)O (C(18)H(27)FeN(10)O(3), a = b = c = 20.2707(5), cubic, I3d, Z = 16), Fe(3).4.5H(2)O (C(18)H(30)FeN(10)O(4.5), a = 20.9986(10), b = 11.7098(5), c = 19.9405(9), beta = 109.141(1), monoclinic, P2(1)/c), Z = 8), and [FeH(3)(3)](ClO(4))(2).H(2)O (C(18)H(26)Cl(2)FeN(10)O(9), a = 9.4848(4), b = 23.2354(9), c = 12.2048(5), beta = 111.147(1) degrees, monoclinic, P2(1)/n, Z = 4) were determined at 100 K. The structures are similar to one another and feature an octahedral iron with facial coordination of imidazoles and imine nitrogen atoms. The iron(III) complexes of the deprotonated ligands, Fe(1), Fe(2), and Fe(3), are low-spin while the protonated iron(III) cationic complexes, [FeH(3)(1)](ClO(4))(3) and [FeH(3)(2)](ClO(4))(3), are high-spin and spin-crossover, respectively. The iron(II) cationic complexes, [FeH(3)(1)]S(4)O(6), [FeH(3)(2)](ClO(4))(2), [FeH(3)(3)](ClO(4))(2), and [FeH(3)(3)][B(C(6)H(5))(4)](2) exhibit spin-crossover behavior. Cyclic voltammetric measurements on the series of complexes show that complete deprotonation of the ligands produces a negative shift in the Fe(III)/Fe(II) reduction potential of 981 mV on average. Deprotonation in air of either cationic iron(II) or iron(III) complexes, [FeH(3)L](3+or2+), yields the neutral iron(III) complex, FeL. The process is reversible for Fe(3), where protonation of Fe(3) yields [FeH(3)(3)](2+).     

Kinetics and mechanism of a catalytic chloride ion effect on the dissociation of model siderophore hydroxamate-iron(III) complexes

Proton-driven ligand dissociation kinetics in the presence of chloride, bromide, and nitrate ions have been investigated for model siderophore complexes of Fe(III) with the mono- and dihydroxamic acid ligands R(1)C(=O)N(OH)R(2) (R(1) = CH(3), R(2) = H; R(1) = CH(3), R(2) = CH(3); R(1) = C(6)H(5), R(2) = H; R(1) = C(6)H(5), R(2) = C(6)H(5)) and CH(3)N(OH)C(=O)[CH(2)](n)C(=O)N(OH)CH(3) (H(2)L(n); n = 2, 4, 6). Significant rate acceleration in the presence of chloride ion is observed for ligand dissociation from the bis(hydroxamate)- and mono(hydroxamate)-bound complexes. Rate acceleration was also observed in the presence of bromide and nitrate ions but to a lesser extent. A mechanism for chloride ion catalysis of ligand dissociation is proposed which involves chloride ion dependent parallel paths with transient Cl(-) coordination to Fe(III). The labilizing effect of Cl(-) results in an increase in microscopic rate constants on the order of 10(2)-10(3). Second-order rate constants for the proton driven dissociation of dinuclear Fe(III) complexes formed with H(2)L(n)() were found to vary with Fe-Fe distance. An analysis of these data permits us to propose a reactive intermediate of the structure (H(2)O)(4)Fe(L(n)())Fe(HL(n))(Cl)(OH(2))(2+) for the chloride ion dependent ligand dissociation path. Environmental and biological implications of chloride ion enhancement of Fe(III)-ligand dissociation reactions are presented.     

Synthesis and characterization of the tetranuclear iron(III) complex of a new asymmetric multidentate ligand. A structural model for purple acid phosphatases

The ligand, 2-((2-hydroxy-5-methyl-3-((pyridin-2-ylmethylamino)methyl)benzyl)(2-hydroxybenzyl)amino)acetic acid (H(3)HPBA), which contains a donor atom set that mimics that of the active site of purple acid phosphatase is described. Reaction of H(3)HPBA with iron(III) or iron(II) salts results in formation of the tetranuclear complex, [Fe(4)(HPBA)(2)(OAc)(2)(mu-O)(mu-OH)(OH(2))(2)]ClO(4) x 5H(2)O. X-Ray structural analysis reveals the cation consists of four iron(III) ions, two HPBA(3-) ligands, two bridging acetate ligands, a bridging oxide ion and a bridging hydroxide ion. Each binucleating HPBA(3-) ligand coordinates two structurally distinct hexacoordinate iron(III) ions. The two metal ions coordinated to a HPBA(3-) ligand are linked to the two iron(III) metal ions of a second, similar binuclear unit by intramolecular oxide and hydroxide bridging moieties to form a tetramer. The complex has been further characterised by elemental analysis, mass spectrometry, UV-vis and MCD spectroscopy, X-ray crystallography, magnetic susceptibility measurements and variable-temperature M?ssbauer spectroscopy.     

The chemistry of dinuclear analogues of the anticancer drug cisplatin. A DFT/CDM study

The mechanism of the formation of dinuclear platinum(II) mu-hydroxo complexes from cisplatin hydrolysis products, their interconversion, decomposition, and reactions with biomolecules has been explored using a combined DFT/CDM approach. All activation barriers for the formation of [cis-{Pt(NH(3))(2)(X)}-(mu-OH)-cis-{Pt(NH(3))(2)(Y)}](n)()(+) (X, Y = Cl, OH(2), OH) via nucleophilic attack of a hydroxo complex on an aqua complex are lower than the activation barriers for cisplatin hydrolysis. Considering therapeutic Pt(II) concentrations in tumors, however, only the reaction between two molecules of cis-[Pt(NH(3))(2)(OH(2))(OH)](+) (E) yielding [cis-{Pt(NH(3))(2)(OH(2))}-(mu-OH)-cis-{Pt(NH(3))(2)(OH)}](2+) (5) remains kinetically superior to cisplatin hydrolysis. 5 is strongly stabilized by intramolecular hydrogen bonding between the terminal aqua and hydroxo ligands, resulting in an unusually high pK(a) of 5 and a low pK(a) of its conjugate acid. Unimolecular cyclization of 5 yields the dimers [cis-{Pt(NH(3))(2)}(mu-OH)](2)(2+) (7a with antiperiplanar OH groups and 7b with synperiplanar OH groups). The electronic structure of several diplatinum(II) complexes has been analyzed to clarify whether there are metal-metal interactions. The overall reactivity to guanine (Gua) and dimethyl sulfide (Met, representing the thioether functional group of methionine) increases in the order 5 < 7a approximately 7b < mononuclear complexes, whereas the kinetic selectivity to Gua relative to Met increases in the order 7a approximately 5 < 7b approximately monocationic mononuclear complexes < dicationic mononuclear complex. The results of this work (i) help assess whether dinuclear metabolites play a role in cisplatin chemotherapy, (ii) elucidate the toxicity and pharmacological inactivity of [cis-{Pt(NH(3))(2)}(mu-OH)](2)(2+), and (iii) suggest future investigations of dinuclear anticancer complexes that contain one mu-hydroxo ligand.     

Aggregation control by homologous tripodal tetradentate amino acid ligands in oxo-bridged diiron(III) aquo complexes

Isoelectronic oxo-bridged diiron(III) aquo complexes of the homologous tripodal tetradentate amino acid ligands, N,N'-bis(2-pyridylmethyl)-3-aminoacetate (bpg(-)) and N,N'-bis(2-pyridylmethyl)-3-aminopropionate (bpp(-)), containing [(H(2)O)Fe(III)-(mu-O)-Fe(III)(H(2)O)](4+) cores, oligomerise, respectively, by dehydration and deprotonation, or by dehydration only, in reversible reactions. In the solid state, [Fe(2)(O)(bpp)(2)(H(2)O)(2)](ClO(4))(2) (1(ClO(4))(2)) exhibits stereochemistry identical to that of [Fe(2)(O)(bpg)(2)(H(2)O)(2)](ClO(4))(2) (2(ClO(4))(2)), with the ligand carboxylate donor oxygen atoms and the water molecules located cis to the oxo bridge and the tertiary amine group trans to it. Despite their structural similarity, 1(2+) and 2(2+) display markedly different aggregation behaviour in solution. In the absence of significant water, 1(2+) dehydrates and dimerises to give the tetranuclear complex, [Fe(4)(O)(2)(bpp)(4)](ClO(4))(4) (3(ClO(4))(4)), in which the carboxylate groups of the four bpp(-) ligands act as bridging groups between two [Fe(2)(O)(bpp)(2)](2+) units. Under similar conditions, 2(2+) dehydrates and deprotonates to form dinuclear and trinuclear oligomers, [Fe(2)(O)(OH)(bpg)(2)](ClO(4)) (4ClO(4)) and [Fe(3)(O)(2)(OH)(bpg)(3)](ClO(4)) (5(ClO(4))), related by addition of 'Fe(O)(bpg)' units. The trinuclear 5(ClO(4)), characterised crystallographically as two solvates 5(ClO(4)).3H(2)O and 5(ClO(4)).2MeOH, is based on a hexagonal [Fe(3)(O)(2)(OH)(bpg)(3)](+) unit, formally containing one hydroxo and two oxo bridges. The different aggregation behaviour of 1(ClO(4))(2) and 2(ClO(4))(2) results from the difference of one methylene group in the pendant carboxylate arms of the amino acid ligands.     

Reactivity of a (mu-oxo)(mu-hydroxo)diiron(III) diamond core with water, urea, substituted ureas, and acetamide

A series of iron(III) complexes of the tetradentate ligand BPMEN (N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)ethane-1,2-diamine) were prepared and structurally characterized. Complex [Fe(2)(mu-O)(mu-OH)(BPMEN)(2)](ClO(4))(3) (1) contains a (mu-oxo)(mu-hydroxo)diiron(III) diamond core. Complex [Fe(BPMEN)(urea)(OEt)](ClO(4))(2) (2) is a rare example of a mononuclear non-heme iron(III) alkoxide complex. Complexes [Fe(2)(mu-O)(mu-OC(NH(2))NH)(BPMEN)(2)](ClO(4))(3) (3) and [Fe(2)(mu-O)(mu-OC(NHMe)NH)(BPMEN)(2)](ClO(4))(3) (4) feature N,O-bridging deprotonated urea ligands. The kinetics and equilibrium of the reactions of 1 with ligands L (L = water, urea, 1-methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, and acetamide) in acetonitrile solutions were studied by stopped-flow UV-vis spectrophotometry, NMR, and mass spectrometry. All these ligands react with 1 in a rapid equilibrium, opening the four-membered Fe(III)(mu-O)(mu-OH)Fe(III) core and forming intermediates with a (HO)Fe(III)(mu-O)Fe(III)(L) core. The entropy and enthalpy for urea binding through oxygen are DeltaH degrees = -25 kJ mol(-1) and DeltaS degrees = -53.4 J mol(-1) K(-1) with an equilibrium constant of K(1) = 37 L mol(-1) at 25 degrees C. Addition of methyl groups on one of the urea nitrogen did not affect this reaction, but the addition of methyl groups on both nitrogens considerably decreased the value of K(1). An opening of the hydroxo bridge in the diamond core complex [Fe(2)(mu-O)(mu-OH)(BPMEN)(2)] is a rapid associative process, with activation enthalpy of about 60 kJ mol(-1) and activation entropies ranging from -25 to -43 J mol(-1) K(-1). For the incoming ligands with the -CONH(2) functionality (urea, 1-methylurea, 1,1-dimethylurea, and acetamide), a second, slow step occurs, leading to the formation of stable N,O-coordinated amidate diiron(III) species such as 3 and 4. The rate of this ring-closure reaction is controlled by the steric bulk of the incoming ligand and by the acidity of the amide group.     

Axial ligand and spin-state influence on the formation and reactivity of hydroperoxo-iron(III) porphyrin complexes

The present study focuses on the formation and reactivity of hydroperoxo-iron(III) porphyrin complexes formed in the [Fe(III)(tpfpp)X]/H(2)O(2)/HOO(-) system (TPFPP=5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin; X=Cl(-) or CF(3) SO(3)(-)) in acetonitrile under basic conditions at -15 °C. Depending on the selected reaction conditions and the active form of the catalyst, the formation of high-spin [Fe(III)(tpfpp)(OOH)] and low-spin [Fe(III)(tpfpp)(OH)(OOH)] could be observed with the application of a low-temperature rapid-scan UV/Vis spectroscopic technique. Axial ligation and the spin state of the iron(III) center control the mode of O-O bond cleavage in the corresponding hydroperoxo porphyrin species. A mechanistic changeover from homo- to heterolytic O-O bond cleavage is observed for high- [Fe(III)(tpfpp)(OOH)] and low-spin [Fe(III)(tpfpp)(OH)(OOH)] complexes, respectively. In contrast to other iron(III) hydroperoxo complexes with electron-rich porphyrin ligands, electron-deficient [Fe(III)(tpfpp)(OH)(OOH)] was stable under relatively mild conditions and could therefore be investigated directly in the oxygenation reactions of selected organic substrates. The very low reactivity of [Fe(III)(tpfpp)(OH)(OOH)] towards organic substrates implied that the ferric hydroperoxo intermediate must be a very sluggish oxidant compared with the iron(IV)-oxo porphyrin π-cation radical intermediate in the catalytic oxygenation reactions of cytochrome P450.     

Structural and spectroscopic features of a cis (hydroxo)-Fe(III)-(carboxylato) configuration as an active site model for lipoxygenases

In our preliminary communication (Ogo, S.; Wada, S.; Watanabe, Y.; Iwase, M.; Wada, A.; Harata, M.; Jitsukawa, K.; Masuda, H.; Einaga, H. Angew. Chem., Int. Ed. 1998, 37, 2102-2104), we reported the first example of X-ray analysis of a mononuclear six-coordinate (hydroxo)iron(III) non-heme complex, [Fe(III)(tnpa)(OH)(RCO(2))]ClO(4) [tnpa = tris(6-neopentylamino-2-pyridylmethyl)amine; for 1, R = C(6)H(5)], which has a characteristic cis (hydroxo)-Fe(III)-(carboxylato) configuration that models the cis (hydroxo)-Fe(III)-(carboxylato) moiety of the proposed (hydroxo)iron(III) species of lipoxygenases. In this full account, we report structural and spectroscopic characterization of the cis (hydroxo)-Fe(III)-(carboxylato) configuration by extending the model complexes from 1 to [Fe(III)(tnpa)(OH)(RCO(2))]ClO(4) (2, R = CH(3); 3, R = H) whose cis (hydroxo)-Fe(III)-(carboxylato) moieties are isotopically labeled by (18)OH(-), (16)OD(-), (18)OD(-), (12)CH(3)(12)C(18)O(2)(-), (12)CH(3)(13)C(16)O(2)(-), (13)CH(3)(12)C(16)O(2)(-), (13)CH(3)(13)C(16)O(2)(-), and H(13)C(16)O(2)(-). Complexes 1-3 are characterized by X-ray analysis, IR, EPR, and UV-vis spectroscopy, and electrospray ionization mass spectrometry (ESI-MS).     

Evaluating the identity and diiron core transformations of a (μ-oxo)diiron(III) complex supported by electron-rich tris(pyridyl-2-methyl)amine ligands

The composition of a (μ-oxo)diiron(III) complex coordinated by tris[(3,5-dimethyl-4-methoxy)pyridyl-2-methyl]amine (R(3)TPA) ligands was investigated. Characterization using a variety of spectroscopic methods and X-ray crystallography indicated that the reaction of iron(III) perchlorate, sodium hydroxide, and R(3)TPA affords [Fe(2)(μ-O)(μ-OH)(R(3)TPA)(2)](ClO(4))(3) (2) rather than the previously reported species [Fe(2)(μ-O)(OH)(H(2)O)(R(3)TPA)(2)](ClO(4))(3) (1). Facile conversion of the (μ-oxo)(μ-hydroxo)diiron(III) core of 2 to the (μ-oxo)(hydroxo)(aqua)diiron(III) core of 1 occurs in the presence of water and at low temperature. When 2 is exposed to wet acetonitrile at room temperature, the CH(3)CN adduct is hydrolyzed to CH(3)COO(-), which forms the compound [Fe(2)(μ-O)(μ-CH(3)COO)(R(3)TPA)(2)](ClO(4))(3) (10). The identity of 10 was confirmed by comparison of its spectroscopic properties with those of an independently prepared sample. To evaluate whether or not 1 and 2 are capable of generating the diiron(IV) species [Fe(2)(μ-O)(OH)(O)(R(3)TPA)(2)](3+) (4), which has previously been generated as a synthetic model for high-valent diiron protein oxygenated intermediates, studies were performed to investigate their reactivity with hydrogen peroxide. Because 2 reacts rapidly with hydrogen peroxide in CH(3)CN but not in CH(3)CN/H(2)O, conditions that favor conversion to 1, complex 1 is not a likely precursor to 4. Compound 4 also forms in the reaction of 2 with H(2)O(2) in solvents lacking a nitrile, suggesting that hydrolysis of CH(3)CN is not involved in the H(2)O(2) activation reaction. These findings shed light on the formation of several diiron complexes of electron-rich R(3)TPA ligands and elaborate on conditions required to generate synthetic models of diiron(IV) protein intermediates with this ligand framework.     

Kinetics and mechanism of iron(III) dissociation from the dihydroxamate siderophores alcaligin and rhodotorulic acid

The kinetics and mechanism of siderophore ligand dissociation from their fully chelated Fe(III) complexes is described for the highly preorganized cyclic tetradentate alcaligin and random linear tetradentate rhodotorulic acid in aqueous solution at 25 degrees C (Fe2L3 + 6H+ reversible 2 Fe3+ aq + 3 H2L). At siderophore:Fe(III) ratios where Fe(III) is hexacoordinated, kinetic data for the H(+)-driven ligand dissociation from the Fe2L3 species is consistent with a singly ligand bridged structure for both the alcaligin and rhodotorulic acid complexes. Proton-driven ligand dissociation is found to proceed via parallel reaction paths for rhodotorulic acid, in contrast with the single path previously observed for the linear trihydroxamate siderophore ferrioxamine B. Parallel paths are also available for ligand dissociation from Fe2(alcaligin)3, although the efficiency of one path is greatly diminished and dissociation of the bis coordinated complex Fe(alcaligin)(OH2)2+ is extremely slow (k = 10(-5) M-1 s-1) due to the high degree of preorganization in the alcaligin siderophore. Mechanistic interpretations were further confirmed by investigating the kinetics of ligand dissociation from the ternary complexes Fe(alcaligin)(L) in aqueous acid where L = N-methylacetohydroxamic acid and glycine hydroxamic acid. The existence of multiple ligand dissociation paths is discussed in the context of siderophore mediated microbial iron transport.     

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)](-).     

On the formation of iron(III) hydroxo acetate complexes

The formation of hydroxo acetate complexes of iron (III) ion has been studied at 25 degrees C in 3 M (Na)ClO4 ionic medium by measuring with a glass electrode the hydrogen ion concentration in Fe(ClO4)3-HClO4-NaAc mixtures (Ac = acetate ion). The acetate/metal ratio ranged from 0 to 6, the metal concentration varied from 0.005 to 0.06 M, whereas [H+] was stepwise decreased from 0.1 M to initial precipitation of hydroxo-acetates. This occurred, depending on the acetate/metal ratio, in the -log[H+] range 1.85-2.7. The potentiometric data are consistent with the presence of Fe3(OH)3Ac3(3+), Fe2(OH)2(4+), Fe3(OH)4(5+), Fe3(OH)5(4+) and, as minor species, of Fe3(OH)2Ac6+, FeAc2+, FeAc2+, FeOH2+ and Fe(OH)2+. Previously published EMF measurements with redox and glass half-cells were recalculated to refine the stability constants of FeAc2+, FeAc2+ and Fe3(OH)2Ac6+. Formation constants *beta pqr for pFe(3+)+(q-r)H2O + rHAc reversible Fep(OH)(q-r)(Ac)r3p-q + qH+ (in parenthesis the infinite dilution value): log*beta 111 = -1.85 +/- 0.02 (-0.67 +/- 0.15), log*beta 122 = -3.43 +/- 0.02 (-1.45 +/- 0.15); log*beta 363 = -5.66 +/- 0.03 (-2.85 +/- 0.40), log*beta 386 = -8.016 +/- 0.006 (-4.06 +/- 0.15), log*beta 220 = -2.88 +/- 0.02 (-2.84 +/- 0.05), log*beta 340 = -6.14 +/- 0.18 (-6.9 +/- 0.4), log*beta 350 = -8.44 +/- 0.09 (-7.65 +/- 0.15).     

Ionic strength dependence of formation constants-XVIII. The hydrolysis of iron(III) in aqueous KNO(3) solutions

The hydrolysis of iron(III) was studied potentiometrically at different ionic strengths in KNO(3) aqueous solutions, at 25 degrees C, to determine the dependence of hydrolysis constants on ionic strength (nitrate media), to check the existence of nitrate-ferric ion interactions, and to confirm the formation of high polymeric species. Under the experimental conditions 0.03 I (KNO(3)) 1M, 0.3 C 12 mM, the species Fe(OH)(2+), Fe(2)(OH)(4+)(2), Fe(OH)(+)(2) and Fe(12)(OH)(2+)(34) were found, and the hydrolysis constants log beta(11) = 2.20, log beta(12) = -2.91, log beta(22) = -5.7, log beta(12,34) = -48.9 (I = 0M) were calculated. The ionic strength dependence of hydrolysis constants is quite close to that found for several protonation and metal complex formation constants reported elsewhere.     

Structural diversity in metal complexes with a dinucleating ligand containing carboxyamidopyridyl groups

The synthesis of a (carboxyamido)pyridinepyrazolate (H(5)bppap) dinucleating ligand is described. Bimetallic iron and cobalt complexes of H(5)bppap ([M(II)(2)H(2)bppap](+)) showed structural differences in both their primary and secondary coordination spheres. The binding of small molecules into the preorganized ligand cavity is verified by the hydration of [Fe(II)(2)H(2)bppap](+) and [Co(II)(2)H(2)bppap](+), leading to the formation of complexes [{Co(II)(OH)}Co(II)H(3)bppap](+) and [{Fe(II)(OH)}Fe(II)H(3)bppap](+), in which one of the metal centers has a terminal hydroxo ligand.