Bis Iron Research Articles

Mechanochemical synthesis of FeCo nanoalloys

The Iron-Cobalt Nanoalloys (ICNAs) were synthesized by co-reduction of the mixture of FeCl2.4H2O and CoCl2.6H2O salts and also in the chemical reduction of iron(II) bis(oxalate)cobaltate pentahydrate complex by aluminum nanoparticles in the solid-state at room temperature. Aluminum nanoparticles were prepared by a novel wire drawing method in the presence of lubricating oil. The products were characterized by IR, XRD, FESEM, EDX and VSM. The absorption bands do not appeared in FTIR spectra of FeCo nanoalloys (ICNAs) while, the spectra of precursor show all the absorption bands of the corresponding complex and salts. The X-ray diffraction pattern results show the presence of two phases unreacted aluminum and FeCo in ICNAs. The weight fraction of FeCo nanoparticles are calculated by the Rietveld method. Quantitative XRD analysis of FeCo-Al (S1) shows a weight fraction of 89.82 % FeCo and unreacted aluminum 10.18 % also, calculation in FeCo-Al (S2) shows weight fraction FeCo and unreacted aluminum 78.50 and 21.50 % respectively. FESEM image of S1 and S2 show maximum particles size distribution in the region of 60 nm to 100 nm and 40 nm to 80 nm respctively. The hysteresis loop of S1 and S2 show magnetic saturation 101.8900 emu/g and 39.6442 emu/g respectively.

A Tetracarbene Iron(II) Complex with a Long‐lived Triplet Metal‐to‐ligand Charge Transfer State due to a Triplet‐Triplet Barrier

Mixed N‐heterocyclic carbene (NHC) / pyridyl iron(II) complexes have attracted a great deal of attention recently because of their potential as photocatalysts and light sensitizers made from Earth‐abundant elements. The most decisive challenge for their successful implementation is the lifetime of the lowest triplet metal‐to‐ligand charge transfer state (3MLCT), which typically decays via a triplet metal‐centered (3MC) state back to the ground state. We reveal by variable‐temperature ultrafast transient absorption spectroscopy that the tripodal iron(II) bis(pyridine) complex isomers trans‐ and cis‐[Fe(pdmi)2]2+with four NHC donors show 3MLCT→3MC population transfers with very different barriers and rationalize this by computational means. While trans‐[Fe(pdmi)2]2+possesses an unobservable activation barrier, the cis isomer exhibits a barrier of 492 cm–1, which leads to a nanosecond 3MLCT lifetime at 77 K. The kinetic and quantum chemical data were analyzed in the context of semi‐classical Marcus theory revealing a high reorganization energy and small electronic coupling between the two triplet states. This highlights the importance of detailed structural control and kinetic knowledge for the rational design of photosensitizers from first row transition metals such as iron.

A Tetracarbene Iron(II) Complex with a Long-lived Triplet Metal-to-Ligand Charge Transfer State due to a Triplet-Triplet Barrier.

Mixed N-heterocyclic carbene (NHC) / pyridyl iron(II) complexes have attracted a great deal of attention recently because of their potential as photocatalysts and light sensitizers made from Earth-abundant elements. The most decisive challenge for their successful implementation is the lifetime of the lowest triplet metal-to-ligand charge transfer state (3MLCT), which typically decays via a triplet metal-centered (3MC) state back to the ground state. We reveal by variable-temperature ultrafast transient absorption spectroscopy that the tripodal iron(II) bis(pyridine) complex isomers trans- and cis-[Fe(pdmi)2]2+ with four NHC donors show 3MLCT→3MC population transfers with very different barriers and rationalize this by computational means. While trans-[Fe(pdmi)2]2+ possesses an unobservable activation barrier, the cis isomer exhibits a barrier of 492 cm-1, which leads to a nanosecond 3MLCT lifetime at 77 K. The kinetic and quantum chemical data were analyzed in the context of semi-classical Marcus theory revealing a high reorganization energy and small electronic coupling between the two triplet states. This highlights the importance of detailed structural control and kinetic knowledge for the rational design of photosensitizers from first row transition metals such as iron.

Iron(I) Complex Bearing an Open-Shell Diazenido Ligand.

Low-valent transition-metal diazenido species are important intermediates in transition-metal-mediated dinitrogen reduction reactions. Isolable complexes of the type unanimously feature closed-shell diazenido ligands. Those bearing open-shell diazenido ligands have remained elusive. Herein, we report the synthesis, characterization, and reactivity of a d7 iron(I) complex featuring an open-shell silyldiazenido ligand, [(ICy)Fe(NNSiiPr3)(η2:η2-dvtms)] (1, ICy = 1,3-dicyclohexylimidazole-2-ylidene, dvtms = divinyltetramethyldisiloxane). Complex 1 is prepared in good yield by silylation of the iron(-I)-N2 complex [K(18-crown-6)][(ICy)Fe(N2)(η2:η2-dvtms)] with iPr3SiOTf and has been fully characterized by various spectroscopic methods. Theoretical studies, in combination with characterization data, established an S = 1/2 ground spin-state for 1 that can best be described as a quartet iron(I) center featuring an antiferromagnetically coupled triplet silyldiazenido ligand. The diazenido and alkene ligands in 1 are labile, as indicated by the facile disproportionation reaction of 1 at ambient temperature to transform into the iron(II) bis(diazenido) species [(ICy)(NNSiiPr3)2Fe(dvtms)Fe(NNSiiPr3)2(ICy)] (2) and the iron(0) species [(ICy)Fe(η2:η2-dvtms)] and also the alkene-exchange reaction of 1 with PhCH═CHBC8H14 to form [(ICy)Fe(NNSiiPr3)(η2-trans-PhCH═CHBC8H14)] (3). Complex 1 is light-sensitive. Upon photolysis, it undergoes a SiiPr3 radical-transfer reaction to yield [(ICy)Fe(σ:η2-MeCHSiMe2OSiMe2CH═CHSiiPr3)] (4) and N2. The reactions of 1 with the trityl radical and organic bromides yield iron(II) complexes, which indicates its reducing nature. Moreover, 1 is a weak hydrogen-atom abstractor, as indicated by its inertness toward HSi(SiMe3)3 and cyclohexa-1,4-diene and the low calculated N-H bond dissociation energy (48 kcal/mol) of its corresponding iron(II) iso-hydrazenido species.

Charge-compensated nido-carborane derivatives in the synthesis of iron(II) bis(dicarbollide) complexes.

A series of stable iron(II) bis(dicarbollide) derivatives [8,8'-(RNHC(Et)HN)2-3,3'-Fe(1,2-C2B9H10)2] (R = Pr, R = Ph, (CH2)2OH, (CH2)3OH, (CH2)2NMe2) was prepared starting from FeCl2 or [FeCl2(dppe)] and the corresponding nido-carboranyl amidines [10-RNHC(Et)HN-7,8-C2B9H11]. In a similar way, the reactions of the oxonium derivatives of nido-carborane with FeCl2 in tetrahydrofuran in the presence of t-BuOK lead to the corresponding stable oxonium derivatives iron(II) bis(dicarbollide) [8,8'-(RR'O)2-3,3'-Fe(1,2-C2B9H10)2] (RR' = (CH2)4, (CH2)2O(CH2)2, (CH2)5; R = R' = Et), which can be alternatively prepared by the reaction of the parent iron(II) bis(dicarbollide) with tetrahydrofuran or 1,4-dioxane in the presence of Me2SO4. The cyclic voltammetry studies of the synthesized iron(II) bis(dicarbollide) derivatives revealed that the introduction of amidinium and oxonium substituents leads to a significant increase in the Fe2+/Fe3+ redox potential relative to the parent iron(II) bis(dicarbollide). The redox potentials of the oxonium derivatives are close to the redox potential of ferrocene and somewhat lower than redox potentials of sulfonium and phosphonium derivatives of iron(II) bis(dicarbollide).

Trigonal bipyramidal or square planar? Density functional theory calculations of iron bis(dithiolene) N-heterocyclic carbene complexes.

Density functional theory (DFT) calculations of 57 iron bis(dithiolene)-N-heterocyclic carbene adducts were conducted to determine what parameters predict, and possibly influence, the coordination of these aforementioned adducts. The parameters considered herein include three different types of nuclear magnetic resonance (C-NMR, Se-NMR, and P-NMR) isotropic chemical shifts, the Tolman Electronic Parameter (TEP), the Huynh Electronic Parameter (HEP), and the percent buried volume (%Vbur) of the different N-heterocyclic carbenes (NHCs) calculated from DFT. These parameters were selected based upon prior literature connection to σ-donor ability, π-acidity, and steric effects. The computed values of the properties were compared via multivariable linear regression models to see which properties best predict the Addison τ parameter-a measure of whether the complex would assume the square pyramidal or trigonal bipyramidal geometry. It was determined that a combination of TEP and %Vbur are the best predictors of the τ value, for the parameters considered herein. The inclusion of additional parameters yields mild improvement to the statistical models for the prediction of the τ value.

Planar three-coordinate iron(II) complexes supported by sterically demanding -Si(SiMe3)2(SiMe2tBu) ligands.

Sterically demanding organosilyl ligands support the formation of coordinatively unsaturated complexes. In this study, we found that using the ligand -Si(SiMe3)2(SiMe2tBu) affords exclusively planar three-coordinate iron bis(silyl) complexes that show good catalytic performance in the hydrosilylation of acetophenone.

Efficacy of Ferrous Bis-Glycinate versus Ferrous Sulphate in Children with Iron Deficiency Anemia

Iron deficiency anemia is a common pediatric disease and oral iron supplementation is the usual treatment. Newer formulations has been developed to treat iron deficiency anemia in children. Objective: To compare the efficacy of ferrous Bis-Glycinate in children with iron deficiency anemia to the conventional therapy with ferrous sulphate. Methods: In this open labelled prospective clinical trial was performed in children with iron deficiency anemia. Two groups were made, one group was given ferrous sulphate and the other group ferrous bis-glycinate at a dose of 5 mg/kg/day, single daily dose. Patient were followed 04 weekly till 12 weeks and then baselines reviewed. Results: Out of these total 108 children, 64 (59.3%) were male while the remaining 40.7% were female, with mean age was 27.48 in months with SD of 14.1. Iron therapy succefully raised Hb by 3.49 gm/dl as a whole with in Iron Bis –glycinate group as 3.85d/dl while 3.13gm /dl in ferrous sulphate group. The frequency of gastrointestinal adverse symptoms were less in bis-glycinate group. Conclusions: It was concluded that ferrous bis-glyicante has better efficacy to ferrous sulphate in term of Hb rising and has less gastrointestinal side effects.

Synthesis, structure determination, NBO analysis and vibrational/electronic spectroscopic study of Iron(II) Bis(diethyldithiocarbamate) [Fe(DDTC)2

This work deals with the synthesis, computational molecular modeling, and vibrational/electronic spectroscopic analysis of the coordination complex [Fe(DDTC)2]. The complex was synthesized according to the guidelines provided by the graphical method. The optimization of the molecular structure was performed using Density Functional Theory with the exchange functional B3LYP and basis set 6–311G(d,p). The experimental FT-IR and Raman spectra of the complex were recorded in the range of 4000–0 cm−1 to correlate them with the calculated spectra. Most of the DFT calculated frequencies agreed with the experimental results, and complete vibrational assignments (including metal-ligand) were made. To investigate the internal electronic mobility of the complex, we performed natural bond orbital analysis (NBO), which provided information regarding intramolecular charge transfer interactions resulting from the overlapping of bonding and antibonding orbitals. The NBO analysis also provided information about the electronic distribution between the HOMO and LUMO orbitals due to charge transfers. We found that the NBO analysis provided the main charge transfers between donor and acceptor atoms, and the HOMO-LUMO energy gap revealed that the complex has high kinetic stability. We also correlated the calculated and experimental UV–Vis spectra to investigate the configurations of several excited states of the complex that involve intra-ligand transitions. The charge transfer and d-d (Laporte Forbidden) bands were assigned. The results also corroborate the existence of several Ligand to Metal Charge Transfer (LMCT) and Metal to Ligand Charge Transfer (MLCT) transitions, as well as d-d transitions. We found that the experimental vibrational spectra agreed with the theoretical ones.

Cobalt and iron bis(dicarbollide) conjugates with cholesterol: synthesis and evaluation of antiproliferative activity

Cobalt and iron bis(dicarbollide) conjugates with cholesterol: synthesis and evaluation of antiproliferative activity

On TAML Catalyst Resting State Lifetimes: Kinetic, Mechanistic, and Theoretical Insight into Phosphate-Induced Demetalation of an Iron(III) Bis(sulfonamido)bis(amido)-TAML Catalyst.

At ambient temperatures, neutral pH and ultralow concentrations (low nM), the bis(sulfonamido)bis(amido) oxidation catalyst [Fe{4-NO2C6H3-1,2-(NCOCMe2NSO2)2CHMe}(OH2)]- (1) has been shown to catalyze the addition of an oxygen atom to microcystin-LR. This persistent bacterial toxin can contaminate surface waters and render drinking water sources unusable when nutrient concentrations favor cyanobacterial blooms. In mechanistic studies of this oxidation, while the pH was controlled with phosphate buffers, it became apparent that iron ejection from 1 becomes increasingly problematic with increasing [phosphate] (0.3-1.0 M); 1 is not noticeably impacted at low concentrations (0.01 M). At pH < 6.5 and [phosphate] ≥ 1.0 M, 1 decays quickly, losing iron from the macrocycle. Iron ejection is surprisingly mechanistically complex; the pseudo-first-order rate constant kobs has an unusual dependence on the total phosphate concentration ([Pt]), kobs = k1[Pt] + k2[Pt]2, indicating two parallel pathways that are first and second order in [phosphate], respectively. The pH profiles in the 5.5-8.3 range for k1 and k2 are different: bell-shaped with a maximum of around pH 7 for k1 and sigmoidal for k2 with higher values at lower pH. Mechanistic proposals for the k1 and k2 pathways are detailed based on both the kinetic data and density functional theory analysis. The major difference between k1 and k2 is the involvement of different phosphate species, i.e., HPO42- (k1) and H2PO4- (k2); HPO42- is less acidic but more nucleophilic, which favors intramolecular rate-limiting Fe-N bond cleavage. Instead, H2PO4- acts intermolecularly, where the kinetics suggest that [H4P2O8]2- drives degradation.

TEMPO and a co-reductant mediated aerobic epoxidation of olefins using a new magnetically recoverable iron(III) bis(phenol)diamine complex: experimental and computational studies.

A magnetically recoverable catalyst of an iron(III) bis(phenol) diamine complex immobilized onto amine functionalized silica-coated magnetic nanoparticles has been synthesized. The catalyst was characterized using FESEM, TEM and XRD which confirmed the nano structure of the catalyst. The physicochemical techniques of ICP, FT-IR, XPS, EDS and TGA proved the loading of the ligand and metal complex on silica-coated magnetic nanoparticles. Using the prepared heterogeneous catalyst, aerobic epoxidation reactions of different alkenes have been investigated in the presence of SO32- as a reducing agent. Moreover, using TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) to discover the mechanism of the aerobic epoxidation of olefins, a new TEMPO-assisted route has been explored. Both of the reaction pathways led to a moderate to high percentage yield of epoxides in water at room temperature. For further understanding mechanistic aspects, density functional theory (DFT) computational studies have been performed. The DFT calculations confirm the suggested mechanism for the title reaction and show the electron density in the vicinity of Fe(II) in the presence of TEMPO as a co-catalyst was more than that in the presence of SO32-.

Four- and three-coordinate planar iron(II) complexes supported by bulky organosilyl ligands.

The ligand exchange reaction of (THF)2Fe[Si(SiMe3)3]2 with 2 equivalents of an N-heterocyclic carbene (NHC) led to the formation of a square-planar iron(II) complex with trans-oriented -Si(SiMe3)3 ligands. Conversely, the introduction of a cis-coordinate bidentate organosilyl ligand instead of -Si(SiMe3)3 resulted in the formation of a square planar iron(II) complex supported by a cis-coordinate bidentate organosilyl ligand. A three-coordinate planar iron(II) bis(silyl) complex was also synthesized using a cis-coordinate bidentate organosilyl ligand and a cyclic (alkyl)(amino)carbene auxiliary ligand. Investigation of the catalytic performance of these complexes in the hydrosilylation of acetophenone revealed that the square-planar iron(II) complex with trans-oriented -Si(SiMe3)3 ligands exhibits superior reactivity relative to its tetrahedral precursor.

Phase transformation from FeSe to Fe3Se4

We report on thermal atomic layer deposition of iron selenide (FeSe and Fe3Se4) thin films with four-inch wafer-scale uniformity using two precursors of iron bis(N, N′-diisopropylacetamidinato) [Fe(i-Pr-Me-AMD)2] and bis(triethysilyl) selenide [(Et3Si)2Se]. The temperature window is determined to be 350–400 °C. The transformation from tetragonal FeSe to monoclinic Fe3Se4 has been found. The tetragonal FeSe thin films exhibit a strong (00 l) texture deposited on amorphous silica glass, suggesting that the surface is partially parallel to the layered ab plane. By adjusting the ratio of iron and selenium, the thin films exhibit from conductors to semiconductors, and finally to insulators. All as-grown conductive samples appear metallic-like temperature dependence by low-temperature electrical transport measurements. This study opens the way to prepare various metal selenides by atomic layer deposition.

Crystal growth, structure elucidation and CHARDI/BVS investigations of β-KCoFe(PO4)2.

Single crystals of β-KCoFe(PO4)2, potassium cobalt(II) iron(III) bis-(ortho-phosphate), were grown from the melt under atmospheric conditions. This phosphate crystallizes isotypically with KZnFe(PO4)2 in space group C2/c, adopting a zeolite-ABW type of structure. The structure of the present phosphate is distinguished by an occupational disorder of the two transition-metal sites with ratios Fe:Co of 0.5725:0.4275 for the first and 0.4275:0.5725 for the second site. In the crystal structure, PO4 and (Co,Fe)O4 tetra-hedra are linked through vertices to form elliptical rings with the sequence DDDDUUUU of up (U) and down (D) pointing vertices. Each eight-membered ring is surrounded by four other rings of the same type, delimiting inter-stices with rectangular shape. This arrangement leads to the formation of [(Co/Fe)(PO4)]- ∞ sheets parallel to (001). Stacking of the sheets into a three-dimensional framework results in the formation of two types of channels. The first one is occupied by potassium cations, whereas the second one remains vacant. Calculations of bond-valence sums and charge distribution were used to confirm the structure model.

Intramolecular rotations and electronic states of iron in the iron bis(dicarbollide) complex Fe[(C2B9H11)2] studied by a 57Fe nuclear probe and computational methods.

Mössbauer spectroscopy of iron(III) bis(dicarbollide) (1) and its adduct (2) revealed low spin FeIII in 1 and surprisingly FeII in 2. In 1, the (C2B9H11) groups rotate at room temperature with a frequency of 107 Hz, getting across the energy barrier of 24 meV. Numerical simulations showed a gradient of electric charge in 2, which may explain the FeII-like character in 2.

An Iron Bis(carbene) Catalyst for Low Overpotential CO2Electroreduction to CO: Mechanistic Insights from Kinetic Zone Diagrams, Spectroscopy, and Theory

An Iron Bis(carbene) Catalyst for Low Overpotential CO₂Electroreduction to CO: Mechanistic Insights from Kinetic Zone Diagrams, Spectroscopy, and Theory

Reactivity of Terminal Iron Borylenes and Bis(borylenes) with Carbodiimides: Cycloaddition, Metathesis, Insertion and C−H Activation Pathways

AbstractThe reactions of carbodiimides with the iron arylborylene complex [Fe=BDur(CO)3(PMe3)] (Dur=2,3,5,6‐Me4C6H) and the iron bis(borylene) complex [Fe{=BDur}{=BN(SiMe3)2}(CO)3] yield a wide variety of temperature‐dependent products, including known FeBNC and novel FeBNB metallacycles, complexes of N‐heterocyclic boracarbene and spiro‐boracarbene ligands and a unique 1,3,2,4‐diazadiborolyl pianostool complex, characterized by NMR spectroscopy and X‐ray crystallography. The product distributions can be rationalized by considering sequences of cycloaddition, metathesis, insertion, and C−H activation pathways mainly governed by sterics.

New Radical-Cation Salts Based on the TMTTF and TMTSF Donors with Iron and Chromium Bis(Dicarbollide) Complexes: Synthesis, Structure, Properties

New radical-cation salts based on tetramethyltetrathiafulvalene (TMTTF) and tetramethyltetraselenefulvalene (TMsTSF) with metallacarborane anions (TMTTF)[3,3′-Cr(1,2-C2B9H11)2], (TMTTF)[3,3′-Fe(1,2-C2B9H11)2], and (TMTSF)2[3,3′-Cr(1,2-C2B9H11)2] were synthesized by electrocrystallization. Their crystal structures were determined by single crystal X-ray diffraction, and their electrophysical properties in a wide temperature range were studied. The first two salts are dielectrics, while the third one is a narrow-gap semiconductor: σRT = 5 × 10−3 Ohm−1cm−1; Ea ≈ 0.04 eV (aprox. 320 cm−1).

Planar Iron Hydride Nanoclusters: Combined Spectroscopic and Theoretical Insights into Structures and Building Principles

The controlled assembly of well‐defined planar nanoclusters from molecular precursors is synthetically challenging and often plagued by the predominant formation of 3D‐structures and nanoparticles. Herein, we report planar iron hydride nanoclusters from reactions of main group element hydrides with iron(II) bis(hexamethyldisilazide). The structures and properties of isolated Fe4, Fe6, and Fe7 nanoplatelets and calculated intermediates enable an unprecedented insight into the underlying building principle and growth mechanism of iron clusters, metal monolayers, and nanoparticles.