A structural and Mössbauer study of complexes with Fe(2)(micro-O(H))(2) cores: stepwise oxidation from Fe(II)(micro-OH)(2)Fe(II) through Fe(II)(micro-OH)(2)Fe(III) to Fe(III)(micro-O)(micro-OH)Fe(III)

Dinuclear non-heme iron clusters containing oxo, hydroxo, or carboxylato bridges are found in a number of enzymes involved in O(2) metabolism such as methane monooxygenase, ribonucleotide reductase, and fatty acid desaturases. Efforts to model structural and/or functional features of the protein-bound clusters have prompted the preparation and study of complexes that contain Fe(micro-O(H))(2)Fe cores. Here we report the structures and spectroscopic properties of a family of diiron complexes with the same tetradentate N4 ligand in one ligand topology, namely [(alpha-BPMCN)(2)Fe(II)(2)(micro-OH)(2)](CF(3)SO(3))(2) (1), [(alpha-BPMCN)(2)Fe(II)Fe(III)(micro-OH)(2)](CF(3)SO(3))(3) (2), and [(alpha-BPMCN)(2)Fe(III)(2)(micro-O)(micro-OH)](CF(3)SO(3))(3) (3) (BPMCN = N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane). Stepwise one-electron oxidations of 1 to 2 and then to 3 demonstrate the versatility of the Fe(micro-O(H))(2)Fe diamond core to support a number of oxidation states with little structural rearrangement. Insight into the electronic structure of 1, 2', and 3 has been obtained from a detailed M?ssbauer investigation (2' differs from 2 in having a different complement of counterions). Mixed-valence complex 2' is ferromagnetically coupled, with J = -15 +/- 5 cm(-)(1) (H = JS(1).S(2)). For the S = (9)/(2) ground multiplet we have determined the zero-field splitting parameter, D(9/2) = -1.5 +/- 0.1 cm(-)(1), and the hyperfine parameters of the ferric and ferrous sites. For T < 12 K, the S = (9)/(2) multiplet has uncommon relaxation behavior. Thus, M(S) = -(9)/(2) <--> M(S) = +(9)/(2) ground state transition is slow while deltaM(S) = +/-1 transitions between equally signed M(S) levels are fast on the time scale of M?ssbauer spectroscopy. Below 100 K, complex 2' is trapped in the Fe(1)(III)Fe(2)(II) ground state; above this temperature, it exhibits thermally assisted electron hopping into the state Fe(1)(II)Fe(2)(III). The temperature dependence of the isomer shifts was corrected for second-order Doppler shift, obtained from the study of diferrous 1. The resultant true shifts were analyzed in a two-state hopping model. The diferric complex 3 is antiferromagnetically coupled with J = 90 +/- 15 cm(-)(1), estimated from a variable-temperature M?ssbauer analysis.     

Synthesis and Magnetic Properties of Fe(II) and Nd(III) Complexes of Poly(N-2-thiazolylacrylamide)

In recent years,the organic ferromagnets have drawn growing attention due to their characteristics of structural diversities,low density,and readily processing1-3.Design and synthesis of magnetic polymers are one of great challenges in today′s magnetic material research,and some significant achievements have been made in this field4,5.In this article,we describe the synthesis of acrylamide-type polymer with pendent thiazolyl groups(Scheme1).The as-prepared polymer exhibited better solubility …     

Synthesis and Characterization of Li(11)Nd(18)Fe(4)O(39-δ)

Li(11)Nd(18)Fe(4)O(39-δ) has been synthesized by the solid-state reaction of pellets, covered with powder of the same composition to avoid lithium loss, with a final reaction temperature of 950 °C. This phase has been reported previously to have various stoichiometries: Li(5)Nd(4)FeO(10), Li(8)Nd(18)Fe(5)O(39), and Li(1.746)Nd(4.494)FeO(9.493). The crystal structure of Li(11)Nd(18)Fe(4)O(39-δ) is closely related to that reported previously for two of the other three compositions but contains extra Li and differences in Li/Fe site occupancies. Fe is present in a mixture of 3+ and 4+ oxidation states, as confirmed by M?ssbauer spectroscopy. The oxygen content of 39 - δ is variable, depending on the processing conditions. Samples slow-cooled in air from 800 °C are semiconducting, attributed to the presence of Fe(4+) ions, whereas samples quenched from 950 °C in N(2) are insulating.     

流动注射分光光度法同时测定Fe(Ⅱ)和Fe(Ⅲ)

将流动注射技术引入邻菲罗啉分光光度法测定Fe2+分析体系,采用单阀双带镀镉锌片还原柱带隔离的阀体流路,建立了同时测定微量Fe2+和Fe3+的分析方法。Fe2+的测定范围为0~10 mg/L,检出限为1.2×10-6mg/L;Fe3+的测定范围为0~12 mg/L,检出限为1.8×10-6mg/L。方法用于水中Fe2+和Fe3+的同时测定。     

Characterization and application of the Fe(II) and α-ketoglutarate dependent hydroxylase FrbJ

The Fe(II) and α-ketoglutarate-dependent hydroxylase FrbJ was previously demonstrated to utilize FR-900098 synthesizing a second phosphonate FR-33289. Here we assessed its ability to hydroxylate other possible substrates, generating a library of potential antimalarial compounds. Through a series of bioassays and in vitro experiments, we identified two new antimalarials.     

Syntheses, structure, and a Mössbauer and magnetic study of Ba(4)Fe(2)I(5)S(4)

The compound Ba4Fe2I5S4 has been prepared at 1223-1123 K by the "U-assisted" reaction of FeS, BaS, S, and U with BaI2 as a flux. A more rational synthesis was also found; however, the presence of U appears to be essential for the formation of single crystals suitable for X-ray diffraction studies. Ba4Fe2I5S4 crystallizes in a new structure type with two formula units in space group I4/m of the tetragonal system. The structure consists of a Ba-I network penetrated by (1)infinity[Fe2S4] chains. Each Fe atom, which is located on a site with 4 symmetry, is tetrahedrally coordinated to four S atoms. The FeS4 tetrahedra edge-share to form linear (1)infinity[Fe2S4] chains in the [001] direction. The Fe-Fe interatomic distance in these chains is 2.5630(4) A, only about 3% longer than the shortest Fe-Fe distance in -Fe metal. Charge balance dictates that the average formal oxidation state of Fe in these chains is +2.5. The M?ssbauer spectra obtained at 85 and 270 K comprise a single quadrupole doublet that has hyperfine parameters consistent with an average Fe oxidation state of +2.5. The M?ssbauer spectrum obtained at 4.2 K consists of a single magnetic sextet with a small hyperfine field of -15.5 T. This spectrum is also consistent with rapid electron delocalization and an average Fe oxidation state of +2.5. The molar magnetic susceptibility of Ba4Fe2I5S4, obtained between 3.4 and 300 K, qualitatively indicates the presence of weak pseudo-one-dimensional ferromagnetic exchange within a linear chain above 100 K and weak three-dimensional ordering between the chains at lower temperatures.     

滴定计算分析法同时测定Fe(Ⅲ)与Fe(Ⅱ)的研究

以铂电极为指示电极,Ce^4 标准溶液为滴定剂,对氧化还原滴定计算分析法同时测定Fe(Ⅲ)与Fe(Ⅱ)进行了研究。导出了同时测定Fe(Ⅲ)与Fe(Ⅱ)的滴定计算式。结果表明,电极的系统误差是影响测定结果准确度的主要因素,而且系统误差对Fe(Ⅲ)的影响比较大,对Fe(Ⅱ)的影响比较小。用刚开始滴定的实验数据,Fe(Ⅲ)的误差比较小;用接近化学计量点的实验数据,Fe(Ⅱ)的误差比较小。     

Characterization of a high-spin non-heme Fe(III)-OOH intermediate and its quantitative conversion to an Fe(IV)═O complex

We have generated a high-spin Fe(III)-OOH complex supported by tetramethylcyclam via protonation of its conjugate base and characterized it in detail using various spectroscopic methods. This Fe(III)-OOH species can be converted quantitatively to an Fe(IV)═O complex via O-O bond cleavage; this is the first example of such a conversion. This conversion is promoted by two factors: the strong Fe(III)-OOH bond, which inhibits Fe-O bond lysis, and the addition of protons, which facilitates O-O bond cleavage. This example provides a synthetic precedent for how O-O bond cleavage of high-spin Fe(III)-peroxo intermediates of non-heme iron enzymes may be promoted.     

Studies on structural and optical properties of pure and transition metals (Ni,Fe and co-doped Ni–Fe) doped tin oxide (SnO2) nanoparticles for anti-microbial activity

Research on Chemical Intermediates - In this present work, pure and transition metal ions (Ni, Fe and co-doped Ni–Fe) doped SnO2 nanoparticles (NPs) were synthesized using a simple chemical...     

Synthesis and relaxivity of Gd(Ⅲ), Fe(Ⅲ) and Mn(Ⅱ) complexes with dihydropyridine derivative of diethvlenetriaminepentaacetic acid

A novel ligand of DTPA-dihydropyridine derivative was synthesized by reaction of DTPA-dianhydride with 4-aniline-1,4-dihydropyridine. Its complexes of gadolinium, manganese and iron were prepared. Their spin-lattice relaxivities (T1) were investigated. The results show that the NMR T1 relaxivitives (R1) for complexes of Fe(Ⅲ), Mn(Ⅱ) are less than that of Gd(Ⅲ) complex, which has a high relaxivity (R1) on the surrounding water protons, indicating that the Gd(Ⅲ) complex possesses the precondition to be contrast agents for magnetic resonance imaging.     

Synthesis and relaxivity of Gd(Ⅲ), Fe(Ⅲ) and Mn(Ⅱ)complexes with dihydropyridine derivative of diethylenetriaminepentaacetic acid

A novel ligand of DTPA-dihydropyridine derivative was synthesized by reaction of DTPA-dianhydride with 4-aniline-1,4-dihydropyridine. Its complexes of gadolinium, manganese and iron were prepared. Their spin-lattice relaxivities (T1) were investigated. The results show that the NMR T1 relaxivitives (R1) for complexes of Fe(Ⅲ), Mn(Ⅱ) are less than that of Gd(Ⅲ) complex,which has a high relaxivity (R1) on the surrounding water protons, indicating that the Gd(Ⅲ) complex possesses the precondition to be contrast agents for magnetic resonance imaging.     

First-principles calculations on the structures,magnetic, and electronic properties of the (Fe2N)m (m = 1–4) and (Fe3N)n (n = 1–3) clusters

The structures, magnetic, and electronic properties of the ground-state (Fe₂N)_m (m?=?1–4) and (Fe₃N)_n (n?=?1–3) clusters have been investigated by using first-principles. The structure of the (Fe₂N)_m and (Fe₃N)_n clusters is a compromise that the N atoms approach more Fe atoms and the N atoms repel each other. The structural stabilities of the (Fe₂N)_m and (Fe₃N)_n clusters increase with the increasing of the N ratio except for the Fe₆N₃ clusters. The (Fe₂N)_m (m?=?1–4) and Fe₉N₃ clusters exhibit more kinetic stabilities than pure iron clusters. The N substitution can decrease the average spin densities of small iron clusters except for the Fe₆N₂ and Fe₈N₄ clusters. The Fe–N bonds exhibit certain covalent bond characteristics.

     

离子色谱法测定大豆种皮提取液中(FeⅡ)和(FeⅢ)

采用国产YSC-1阳离子分离柱,用pH 4的草酸、柠檬酸、醋酸钠和亚硫酸钠溶液为淋洗液,用邻菲啰啉、盐酸羟胺为显色剂,测定了大豆种皮提取液中的Fe(Ⅱ)和Fe(Ⅲ)。     

溶液中Fe(VI)向Fe(IV)转化反应的分光光度法跟踪

Different concentrations of ferrate(VI) with ClO^- and without ClO^- in alkaline solution were traced by visible spectrometry, and the conversion reaction of Fe(VI) to Fe(IV) was found to exist, in condition that c was ≥ 6 mol·L^-1. ClO^- would slow down the decomposition reaction rate of Ferrate(VI) and increase the product concentration of Fe(IV) in the system.     

Fe(Ⅲ)-XO-OP胶束增敏光度法测定水中的痕量Fe(Ⅲ)

以HAc -NaAc为缓冲溶液 (pH =3.2 ) ,二甲酚橙与铁形成紫红色的配合物 ,最大吸收波长为 5 70nm ,在表面活性剂OP存在时 ,配合物的最大吸收波长红移至 5 90nm ,表观摩尔吸光系数由 3.0 4× 10 4L/ (mol·cm)增至 3.6 7×10 5L/ (mol·cm) ,铁的质量浓度在 0～ 2 0 .0 μg/ (2 5mL)内符合比耳定律。该法用于水样中微量铁的测定 ,铁的回收率为 99.8%～ 10 0 .2 % ,测定结果的相对标准偏差为 0 .16 0 %～ 0 .16 6 %。     

Cyanide-bridged bi- and trinuclear heterobimetallic Fe(III)–Mn(III) complexes: Synthesis,crystal structures and magnetic properties

By employing trans-dicyano or pentacyanometalate as building block and using a bicompartimental Schiffbase based manganese(III) compound as assemble segment, two new cyanide-bridged heterometallic Fe(III)–Mn(III) complexes {[Mn(L)(H₂O)][Febpb(CN)₂]}·2CH₃OH (1) and {[Mn(L)(H₂O)]₂··[Fe(CN)₅NO]} (2) (bpb^2– = 1,2-bis(pyridine-2-carboxamido)benzenate, L = N,N'-ethylene-bis(3-ethoxysalicylideneiminate) have been synthesized and characterized by elemental analysis, IR spectroscopy and X-ray structure determination. Single X-ray diffraction analysis reveals binuclear FeMn and trinuclear FeMn₂ structure, respectively, in which the cyanide precursor acts as mono- or bidentate ligand to connect the Mn(III) Schiff-base unit(s). Furthermore, these two complexes are self-complementary through coordinated aqua ligands from one complex and the free O₄ compartments from the neighboring complex, giving dimeric and 1D single chain supramolecular structure. Investigation of the magnetic susceptibility of 1 reveals weak antiferromagnetic coupling between the adjacent Mn(III) ions. Based on the binuclear FeMn model, best fit of the magnetic susceptibilities of 1 leads to the magnetic coupling constants J =–1.37 cm^–1 and zJ′ =–0.72 cm^–1 (1).     

Synthesis and X-ray crystal structure analysis of Fe2(CO)6(μ3-S)2Pd(bipy)

The reaction of Fe₂(CO)₆(μ-S₂),1 withbis(dibenzylideneacetone)-palladium, Pd(dba)₂, in the presence of 2,2′-bipyridine yielded the new compound Fe₂(CO)₆(μ ₃-S)₂Pd(bipy),2 in good yield (66%). Compound2 was characterized by IR,¹H NMR and single-crystal X-ray diffraction analyses. Compound2 contains a Pd(bipy) group that has been inserted into the S-S bond of1. Crystal data for2: space group P2₁/n,a=10.019(2) Å,b=25.414(5) Å,c=7.714(2) Å,β=90.26(2)°,Z=4, 1436 reflections,R=0.023.     

溶液中Fe(Ⅵ)向Fe(Ⅳ)转化反应的分光光度法跟踪

Fe(Ⅵ)化合物因其强氧化性所展现的光明应用前景,正成为研究热点[1].相比之下,对Fe(Ⅳ)化合物人们却知之不多.据文献[2]报道,Fe(Ⅵ)化合物在高碱度溶液中呈绿色,且能稳定存在.通常被称作高铁酸盐的FeⅥ)化合物在碱性溶液中以FeO42-形式存在而呈紫色,高浓度时不稳定,在酸、碱介质中均会分解放出氧气并生成Fe3+或Fe(OH)3.本文采用分光光度法跟踪监测碱性溶液中Fe(Ⅵ)化合物的分解过程,发现除生成Fe(OH)3外,还有Fe(Ⅳ)化合物的绿色溶液生成.在此基础上,对完成这一转化的条件进行了研究,取得了有益的结果,从而深化了对Fe(Ⅵ)和Fe(Ⅳ)化合物重要性质的认识.