Dinuclear Iron Research Articles

Synthesis, Properties, and Electrochemistry of bis(iminophosphorane)pyridine Iron(II) Pincer Complexes

Iron derivatives have emerged as valuable catalysts for a variety of transformations, as well as for biological and photophysical applications, and iminophosphorane can be considered an ideal ligand scaffold for modulating electronic and steric parameters in transition metal complexes. In this report, we aimed to synthesize dichloride and dibromide iron(II) complexes supported by symmetric bis(iminophosphorane)pyridine ligands, starting from readily available ferrous halides. The ease of synthesis of this class of ligands served to access several derivatives with distinct electronic and steric properties imparted by the phosphine moiety. The ligands and the resulting iron(II) complexes were characterized by 31P and 1H NMR spectroscopy and DART or ESI mass spectrometry. While none of these iron(II) complexes could be characterized by single-crystal X-ray diffraction, suitable crystals of a µ-O bridged dinuclear iron complex bearing an iminophosphorane ligand were obtained, confirming a κ3 binding motif. The bis(iminophosphorane)pyridine ligands in the obtained iron(II) complexes are labile, as demonstrated by their facile substitution by terpyridine. Cyclic voltammetry studies revealed that the oxidation of bis(iminophosphorane)pyridine iron(II) complexes to iron(III) species is quasi-reversible, suggesting the strong thermodynamic stabilization of the iron(III) center imparted by the σ-donating iminophosphorane ligands.

Azo-Cyanamide Bridged Dinuclear Iron Complexes Exhibiting no Electronic Coupling but Moderate Magnetic Coupling between the two Iron Centers.

To investigate the effect of long-distance organic ligand on electronic coupling between metallic atoms, the mononuclear and dinuclear complexes [Cp(dppe)Fe(apc)] (1), [{Cp(dppe)Fe}2(μ-adpc)] (2), [{CpMe5(dppe)Fe}2(μ-adpc) (3) and their oxidized complexes [Cp(dppe)Fe(apc)][PF6] (1[PF6]), [{Cp(dppe)Fe}2(μ-adpc)][PF6] (2[PF6]2), [{CpMe5(dppe)Fe}2(μ-adpc)][PF6]2 (3[PF6]2) (Cp=1,3-cyclopentadiene, CpMe5=1,2,3,4,5-pentamethylcyclopentadiene, dppe=1,2-bis(diphenylphosphino)ethane), apc-=4-azo(phenylcyanamido)benzene and adpc2-=4,4'-azodi(phenylcyanamido)) were synthesized and characterized by cyclic voltammetry, UV-vis, single-crystal X-ray diffraction and Mössbauer spectra. Electrochemical measurements showed no electronic coupling between the two terminal Fe units, However, the investigation results of the magnetic properties of the two-electron oxidized complexes indicate the presence of moderate antiferromagnetic coupling across 18 Å distance.

Spin crossover in dinuclear iron(II) complexes bridged by bis-bipyridine ligands: dimer effects on electronic structure, spectroscopic properties and spin-state switching.

Inspired by the well-studied mononuclear spin crossover compound [Fe(H2B(pz)2)2(bipy)], the bipyridine-based bisbidentate ligands 1,2-di(2,2'-bipyridin-5-yl)ethyne (ac(bipy)2) and 1,4-di(2,2'-bipyridine-5-yl)-3,5-dimethoxybenzene (Ph(OMe)2(bipy)2) are used to bridge two [Fe(H2B(pz)2)2] units, leading to the charge-neutral dinuclear iron(II) compounds [{Fe(H2B(pz)2)2}2 μ-(ac(bipy)2)] (1) and [{Fe(H2B(pz)2)2}2 μ-(Ph(OMe)2(bipy)2)] (2), respectively. The spin-crossover properties of these molecules are investigated by temperature-dependent PPMS measurements, Mössbauer, vibrational and UV/Vis spectroscopy as well as X-ray absorption spectroscopy. While compound 1 undergoes complete SCO with T1/2 = 125 K, an incomplete spin transition is observed for 2 with an inflection point at 152 K and a remaining high-spin fraction of 40% below 65 K. The spin transitions of the dinuclear compounds are also more gradual than for the parent compound [Fe(H2B(pz)2)2(bipy)]. This is attributed to steric hindrance between the molecules, limiting intermolecular interactions such as π-π-stacking.

Helical dinuclear 3d metal complexes with bis(bidentate) [S,N] ligands: synthesis, structural and computational studies.

A diprotic bis(β-thioketoimine) ligand precursor featuring a flexible 4,4'-methylbis(aniline) linker, H22, was synthesised via treatment of the corresponding bis(β-ketoimine) with Lawesson's reagent. Lithiation of H22 and coordination with one equivalent of d-block metal(II) chlorides MCl2(THF)x (M = Fe, Co and Zn) yielded a corresponding series of homoleptic dinuclear complexes, [M2(μ-2)2]. X-ray diffraction analysis reveals a tetrahedral geometry for the two metals and a double-stranded helicate structure arising from inter-strand face-face π-stacking. These interactions create a helical 'twist' of ca. 70°. Utilising a bulky mononucleating β-thioketoiminate ligand, [3]-, the analogous series of homoleptic monometallic complexes, [M(3)2] (M = Fe, Co and Zn), were prepared and characterised by spectroscopic and analytical techniques. A comprehensive DFT study of all complexes reveals a stronger M-S bonding compared to M-N due to a higher degree of covalency. Solution magnetic studies and natural bonding orbital calculations on the mono- and dinuclear iron and cobalt complexes are consistent with high-spin tetrahedral Fe(II) and Co(II) centres, and cyclic voltammetry reveals both oxidation and reduction processes are accessible.

O-O bond formation via radical coupling in a dinuclear iron water oxidation catalyst with high catalytic activity.

The use of iron-based catalysts for the water oxidation reaction is highly attractive due to the high abundance of iron. While many molecular catalysts have been made, most show limited activity and short lifetimes. An exception with higher activity was presented by Thummel and co-workers in 2015. Herein we present a study on the feasibility of the coupling of two O centered radicals originating from the two subunits of the dinuclear catalyst. The reaction pathway includes the oxidation to the active species FeIV-O-FeIV but avoids further high potential oxidations which previous mechanistic proposals have relied on.

In-situ synthesis of dinuclear Iron (III) complex; Crystal structure, DFT calculations, Hirshfield surface analysis, and molecular docking

A one-pot reaction of 2-pyridincarboxyaldehyde, 2-amino-1,3-propandiol, FeCl3 and NaN3 in MeOH leading to an in-situ oxazolidine ligand formation enabled the preparation of a new dimeric complex [Fe2(pdom)2(N3)4 (1), where (pdom)− is (2-(pyridin-2-yl)-4,5-dihydrooxazol-4-yl)methanol (pdomH) ligand. Complex 1 was characterised by infrared spectroscopy, elemental analysis and single crystal X-ray diffraction. The structural analysis indicates that 1 is a centrosymmetic molecule where two Fe (III) are bridged by two (pdom)− ligands. The theoretical study of 1 was carried out to assess the structural properties of the complex where the non-covalent interactions and the data indicate good agreement between the theoretical and experimental results. From the density functional theory (DFT) calculations, it was determined that complex 1 adopts the triplet state. In order to get an insight into the possible biological activity of the complex, molecular docking of complex 1 was performed with the DNA topoisomerase I (TOP1), and various conformations of 1 bound with TOP1 were analysed in terms of energy, hydrogen-bonding and hydrophobic interaction. NCI analysis has been investigated to shows its bonding nature. The docking study reveals that complex 1 binds proficiently with TOP1 along the major groove of the DNA with a free energy of 11.72 kcal mol−1, and hydrogen bonds, as calculated by Hirshfeld analysis, are responsible for promoting binding with DNA.

Repurposing Iron‐ and 2‐Oxoglutarate‐Dependent Oxygenases to Catalyze Olefin Hydration

AbstractMononuclear nonheme iron(II) and 2‐oxoglutarate (Fe/2OG)‐dependent oxygenases and halogenases are known to catalyze a diverse set of oxidative reactions, including hydroxylation, halogenation, epoxidation, and desaturation in primary metabolism and natural product maturation. However, their use in abiotic transformations has mainly been limited to C−H oxidation. Herein, we show that various enzymes of this family, when reconstituted with Fe(II) or Fe(III), can catalyze Mukaiyama hydration—a redox neutral transformation. Distinct from the native reactions of the Fe/2OG enzymes, wherein oxygen atom transfer (OAT) catalyzed by an iron‐oxo species is involved, this nonnative transformation proceeds through a hydrogen atom transfer (HAT) pathway in a 2OG‐independent manner. Additionally, in contrast to conventional inorganic catalysts, wherein a dinuclear iron species is responsible for HAT, the Fe/2OG enzymes exploit a mononuclear iron center to support this reaction. Collectively, our work demonstrates that Fe/2OG enzymes have utility in catalysis beyond the current scope of catalytic oxidation.

Repurposing Iron- and 2-Oxoglutarate-Dependent Oxygenases to Catalyze Olefin Hydration.

Mononuclear nonheme iron(II) and 2-oxoglutarate (Fe/2OG)-dependent oxygenases and halogenases are known to catalyze a diverse set of oxidative reactions, including hydroxylation, halogenation, epoxidation, and desaturation in primary metabolism and natural product maturation. However, their use in abiotic transformations has mainly been limited to C-H oxidation. Herein, we show that various enzymes of this family, when reconstituted with Fe(II) or Fe(III), can catalyze Mukaiyama hydration-a redox neutral transformation. Distinct from the native reactions of the Fe/2OG enzymes, wherein oxygen atom transfer (OAT) catalyzed by an iron-oxo species is involved, this nonnative transformation proceeds through a hydrogen atom transfer (HAT) pathway in a 2OG-independent manner. Additionally, in contrast to conventional inorganic catalysts, wherein a dinuclear iron species is responsible for HAT, the Fe/2OG enzymes exploit a mononuclear iron center to support this reaction. Collectively, our work demonstrates that Fe/2OG enzymes have utility in catalysis beyond the current scope of catalytic oxidation.

Magnetic properties of an oxo-bridged dinuclear iron(III) complex resulting from the oxidation of mononuclear iron metallacycles with a flexible ethylenediphenylenebis(oxamate) ligand

Transition metal ions such as copper(II), nickel(II), cobalt(II), and manganese(II) are widely used in the formation of mono- or oligonuclear metallacyclic complexes with the flexible N,N’-2,2′-ethylenediphenylenebis(oxamate) ligand (H4edpba); however similar supramolecular complexes with iron(II) and iron(III) are rarely obtained. In this work, we synthesized for the first time a new air-stable oxo-bridged diiron(III) complex of formula {[Fe(H2edpba)(dmso)]2(μ-O)}·dmso·H2O (2) from dioxygen oxidation of the putative mononuclear iron(II) complex precursor of formula [Fe(H2edpba)(H2O)2]Cl (1) in dimethylsulfoxide (dmso). Compound 2 crystallizes in the monoclinic system and contains one oxo group bridging two cationic mononuclear metallacyclic moieties, [Fe(H2edpba)(dmso)]+. The iron(III) ions are also coordinated to four oxygen atoms from the dianionic H2edpba2− ligands in a tetradentate fashion, while an oxygen atom from the coordinated dmso molecules. Mössbauer spectroscopy confirms the presence of high-spin (HS) Fe3+ ions (2). The magnetic properties of 2 reveal a strong antiferromagnetic interaction between the two HS Fe3+ ions (J = −226.46 cm−1), in agreement with the DFT calculations (J = −207.99 cm−1).

Dinuclear Iron(II) Triple Helicates Exhibiting Room Temperature Spin-Transition Behaviour in Solid and Solution Phase.

Herein, three dinuclear iron(II) helicates bearing the molecular formula [Fe2 (L1)3 ](ClO4 )4 ⋅ 2CH3 OH ⋅ 3H2 O (complex 1), [Fe2 (L2)3 ](ClO4 )4 ⋅ 6CH3 CN (complex 2), and [Fe2 (L3)3 ](ClO4 )4 ⋅ 0.5H2 O (complex 3) have been synthesized using imidazole and pyridine-imine-based ligands having fluorene moiety in the backbone. A change in the ligand field strength by terminal modulation led to a change in the spin-transition behaviour from incomplete, multi-step to complete, around room temperature in the solid state. Spin transition behaviour has also been observed in the solution phase characterized using variable temperature 1 H nuclear magnetic resonance spectroscopy (Evans method) and correlated using UV-visible spectroscopy. Fitting the NMR data using the ideal solution model yielded the transition temperature in the order T1/2 (1)<T1/2 (2)<T1/2 (3), which indicates an increase in the ligand field strength from complexes 1 to 3. This study accentuates the interplay between the ligand field strength, crystal packing, and supramolecular interactions in fine-tuning the spin transition behaviour effectively.

Photochemical CO2 Reduction to CO Catalyzed by a Doubly N-Confused Hexaphyrin Dinuclear Iron Complex

In the quest for efficient catalysts for the CO2 reduction reaction, a doubly N-confused hexaphyrin (DNCH) dinuclear iron complex, [(FeCl)2(DNCH)], was found to be catalytically active in the photochemical CO2 reduction reaction. Electrochemical and spectroelectrochemical measurements revealed that the DNCH ligand functions as a redox center in the CO2 reduction reaction.

Iron-tracking strategies: Chaperones capture iron in the cytosolic labile iron pool.

Cells express hundreds of iron-dependent enzymes that rely on the iron cofactors heme, iron-sulfur clusters, and mono-or di-nuclear iron centers for activity. Cells require systems for both the assembly and the distribution of iron cofactors to their cognate enzymes. Proteins involved in the binding and trafficking of iron ions in the cytosol, called cytosolic iron chaperones, have been identified and characterized in mammalian cells. The first identified iron chaperone, poly C-binding protein 1 (PCBP1), has also been studied in mice using genetic models of conditional deletion in tissues specialized for iron handling. Studies of iron trafficking in mouse tissues have necessitated the development of new approaches, which have revealed new roles for PCBP1 in the management of cytosolic iron. These approaches can be applied to investigate use of other nutrient metals in mammals.

Comparative oxidative ability of mononuclear and dinuclear high-valent iron-oxo species towards the activation of methane: does the axial/bridge atom modulate the reactivity?

Over the years, mononuclear FeIVO species have been extensively studied, but the presence of dinuclear FeIVO species in soluble methane monooxygenase (sMMO) has inspired the development of biomimic models that could activate inert substrates such as methane. There are some successful attempts; particularly the [(Por)(m-CBA) FeIV(μ-N)FeIV(O)(Por˙+)]- species has been reported to activate methane and yield decent catalytic turnover numbers and therefore regarded as the closest to the sMMO enzyme functional model, as no mononuclear FeIVO analogues could achieve this feat. In this work, we have studied a series of mono and dinuclear models using DFT and ab initio DLPNO-CCSD(T) calculations to probe the importance of nuclearity in enhancing the reactivity. We have probed the catalytic activities of four complexes: [(HO)FeIV(O)(Por)]- (1), [(HO)FeIV(O)(Por˙+)] (2), μ-oxo dinuclear iron species [(Por)(m-CBA)FeIV(μ-O)FeIV(O) (Por˙+)]- (3) and N-bridged dinuclear iron species [(Por)(m-CBA)FeIV(μ-N)FeIV(O)(Por˙+)]- (4) towards the activation of methane. Additionally, calculations were performed on the mononuclear models [(X)FeIV(O)(Por˙+)]n {X = N 4a (n = -2), NH 4b (n = -1) and NH24c (n = 0)} to understand the role of nuclearity in the reactivity. DFT calculations performed on species 1-4 suggest an interesting variation among them, with species 1-3 possessing an intermediate spin (S = 1) as a ground state and species 4 possessing a high-spin (S = 2) as a ground state. Furthermore, the two FeIV centres in species 3 and 4 are antiferromagnetically coupled, yielding a singlet state with a distinct difference in their electronic structure. On the other hand, species 2 exhibits a ferromagnetic coupling between the FeIV and the Por˙+ moiety. Our calculations suggest that the higher barriers for the C-H bond activation of methane and the rebound step for species 1 and 3 are very high in energy, rendering them unreactive towards methane, while species 2 and 4 have lower barriers, suggesting their reactivity towards methane. Studies on the system reveal that model 4a has multiple FeN bonds facilitating greater reactivity, whereas the other two models have longer Fe-N bonds and less radical character with steeper barriers. Strong electronic cooperativity is found to be facilitated by the bridging nitride atom, and this cooperativity is suppressed by substituents such as oxygen, rendering them inactive. Thus, our study unravels that apart from enhancing the nuclearity, bridging atoms that facilitate strong cooperation between the metals are required to activate very inert substrates such as methane, and our results are broadly in agreement with earlier experimental findings.

A closed-shell phenalenyl-based dinuclear iron(III) complex as a robust cathode for a one-compartment H2O2 fuel cell.

Closed-shell phenalenyl (PLY) systems are increasingly becoming more attractive as building blocks for developing promising catalysts and electroactive cathode materials, as they have tremendous potential to accept electrons and participate in redox reactions. Herein, we report a PLY-based dinuclear [FeIII2(hmbh-PLY)3] complex, 1, and its utility as a cathode material in a H2O2 fuel cell. Complex 1 was synthesized from a new Schiff base ligand, (E)-9-(2-(2-hydroxy-3-methoxybenzylidene)hydrazineyl)-1H-phenalen-1-one, hmbh-PLYH2, designed using a PLY precursor, Hz-PLY. The newly derived ligand and complex 1 were characterized by various analytical techniques, including single-crystal X-ray diffraction (SCXRD). The cyclic voltammetry (CV) study revealed that complex 1 undergoes five electron reductions under an applied electric potential. When the electroactive complex 1 was employed as a cathode in a membrane-less one-compartment H2O2 fuel cell, with Ni foam as the corresponding anode, the designed fuel cell exhibited an exceptionally high peak power density (PPD) of 2.41 mW cm-2, in comparison with those of all the previously reported Fe-based molecular complexes. DFT studies were performed to gain reasonable insights into the two-electron catalytic reduction (pathway I) of H2O2 by the Fe-center of complex 1 and to explore the geometries, energetics of the electrocatalyst, reactive intermediates and transition states.

Stability and reactivity of dinuclear iron(III)-salen complexes as catalysts in ethylene polymerization: A computational approach

The increasing demand for olefin polymers has prompted extensive research on catalysis, processes, and structural characterization to explore their economic potential. In this study, N,N'-bis(salicylidene)-1,2-ethylenediamine (salen) was synthesized, complexed with Fe(III) ion, and the complex was bridged by simple condensation reaction with five different dicarboxylic acids to produce dinuclear complexes. Different methods, such as 1H NMR, FT-IR, UV–Vis, and EDX elemental analysis, were used to analyze and identify the ligand and complexes. Spectroscopic results supported by molecular modeling studies, revealed that the complexes had an octahedral geometry. Structural optimization of the ligand and metal complexes was performed using Avogadro (version 1.2.0) and the Universal Force Field molecular mechanics level. Density functional theory was used to conduct computational calculations on the stability and reactivity of the zeolite-supported and unsupported complexes as catalysts for the polymerization of ethylene. Interestingly, the supported complexes were found to exhibit lower stability and higher reactivity than the neat metal complexes. As such, the synthesized complexes are promising catalysts for the production of polyethylene, and their use could significantly reduce the cost of industrial polyethylene production.

A metal-organic framework-supported dinuclear iron catalyst for hydroboration of carbonyl compounds.

Preparation of catalytically active dinuclear transition metal complexes with an open coordination sphere is a challenging task because the metal sites tend to be "saturated" with excess donor atoms around during synthesis. By isolating the binding scaffolds with the metal-organic framework (MOF) skeleton and installing metal sites through post-synthetic modification, we succeed in constructing a MOF-supported metal catalyst, namely FICN-7-Fe2, with dinuclear Fe2 sites. FICN-7-Fe2 effectively catalyses the hydroboration of a broad range of ketone, aldehyde, and imine substrates with a low loading of 0.05 mol%. Remarkably, kinetic measurements showed that FICN-7-Fe2 is 15 times more active than its mononuclear counterpart FICN-7-Fe1, indicating that cooperative substrate activation on the two Fe centres significantly enhances the catalysis.

Dinuclear Iron Complexes of Iminopyridine-Based Ligands as Selective Cytotoxins for Tumor Cells and Inhibitors of Cancer Cell Migration.

A family of dinuclear iron (II) compounds with iminopyridine-based ligands displays selective cytotoxic activity against cancer cell lines. All compounds have IC50 values 2-6 fold lower than that of cisplatin, and 30-90 fold lower than that of carboplatin for the tumor cell lines assayed. Comparing the IC50 values between tumor and non-tumor cell lines, the selectivity indexes range from 3.2 to 34, compound 10, [Fe2(4)2(CH3CN)4](BF4)4, showing the highest selectivity. Those compounds carrying substituents on the iminopyridine ring show the same cytotoxicity as those without substituents. However, the electronic effects of the substituents on position 6 may be important for the cytotoxicity of the complexes, and consequently for their selectivity. All compounds act over DNA, promoting cuts on both strands in the presence of reactive oxygen species. Since compound 10 presented the highest selectivity, its cytotoxic effect was further characterized. It induces apoptosis, affects cell cycle phase distribution in a cell-dependent manner, and its cytotoxic effect is linked to reactive oxygen species generation. In addition, it decreases tumor cell migration, showing potential antimetastatic effects. These properties make compound 10 a good lead antitumor agent among all compounds studied here.

Synthesis and Complexation Study of New Aminoalkynyl−amidinate Ligands

AbstractThe current library of amidinate ligands has been extended by the synthesis of two novel dimethylamino‐substituted alkynylamidinate anions of the composition [Me2N−CH2−C≡C−C(NR)2]−(R =iPr, cyclohexyl (Cy)). The unsolvated lithium derivatives Li[Me2N−CH2−C≡C−C(NR)2] (1: R =iPr,2: R = Cy) were obtained in good yields by treatment ofin situ‐prepared Me2N−CH2−C≡C−Li with the respective carbodiimides, R−N=C=N−R. Recrystallization of1and2from THF afforded the crystalline THF adducts Li[Me2N−CH2−C≡C−C(NR)2] ⋅ nTHF (1 a: R =iPr,n=1;2 a: R = Cy,n=1.5). Precursor2was subsequently used to study initial complexation reactions with selected di‐ and trivalent transition metals. The dark red homoleptic vanadium(III) tris(alkynylamidinate) complex V[Me2N−CH2−C≡C−C(NCy)2]3(3) was prepared by reaction of VCl3(THF)3with 3 equiv. of2(75 % yield). A salt‐metathesis reaction of2with anhydrous FeCl2in a molar ratio of 2 : 1 afforded the dinuclear homoleptic iron(II) alkynylamidinate complex Fe2[Me2N−CH2−C≡C−C(NCy)2]4(4) in 69 % isolated yield. Similarly, treatment of Mo2(OAc)4with 3 or 4 equiv. of2provided the dinuclear, heteroleptic molybdenum(II) amidinate complex Mo2(OAc)[Me2N−CH2−C≡C−C(NCy)2]3(5; yellow crystals, 50 % isolated yield). The cyclohexyl‐substituted title compounds2 a,4, and5were structurally characterized through single‐crystal X‐ray diffraction studies.

Formation of dimethoxy bridged dinuclear iron(III) complex of pyridoxal Schiff base with iron-catalyzed oxidative C[sbnd]N bond cleavage – Structure, magnetic properties, and DFT calculations

Mononuclear Fe(III) complex [FeL(N3)]·CH3OH, where L2– is the dianion of an unsymmetrical propyl-ethyl pentadentate Schiff base ligand condensed from pyridoxal and N-(2-aminoethyl)propane-1,3-diamine, and dinuclear Fe(III) complex [{FeL’}2(μ-OCH3)2]·2.5CH3OH·H2O, where L’2– is the dianion of tetradentate Schiff base ligand based on pyridoxal and ethylenediamine, have been synthesized and characterized by elemental analysis, X-ray structural analysis, FT-IR and mass spectrometry. Tetradentate pyridoxal Schiff base ligand L’2– of the dinuclear complex was generated in situ via iron-catalyzed oxidative CN bond cleavage of the pentadentate Schiff base. The coordination geometry around the iron(III) centers of the complexes can be described as adistorted octahedron. Magnetic investigations of [FeL(N3)]·CH3OH complex revealed that the octahedral Fe(III) center retains high-spin in the entire temperature range (2–300 K) and enabled the evaluation of the axial zero-field splitting (ZFS) parameter D = –1.78 cm−1, intermolecular exchange parameter zj́ = –1.35 cm−1 and temperature-independent paramagnetism χTIM = 0.00029 cm3mol−1. Magnetic investigations of [{FeL’}2(μ-OCH3)2]·2.5CH3OH·H2O showed that Fe(III) centers are coupled by a strong antiferromagnetic interaction (J = –94.5 cm−1). The experimental magnetic properties of the complexes were compared with the data obtained from the density functional theory (DFT) calculations.

Atmospheric-Pressure Conversion of CO2 to Cyclic Carbonates over Constrained Dinuclear Iron Catalysts.

The conversion of CO2 and epoxides to cyclic carbonates over a silica-supported di-iron(III) complex having a reduced Robson macrocycle ligand system is shown to proceed at 1 atm and 80 °C, exclusively producing the cis-cyclohexene carbonate from cyclohexene oxide. We examine the effect of immobilization configuration to show that the complex grafted in a semirigid configuration catalytically outperforms the rigid, flexible configurations and even the homogeneous counterparts. Using the semirigid catalyst, we are able to obtain a TON of up to 800 and a TOF of up to 37 h–1 under 1 atm CO2. The catalyst is shown to be recyclable with only minor leaching and no change to product selectivity. We further examine a range of epoxides with varying electron-withdrawing/donating properties. This work highlights the benefit arising from the constraining effect of a solid surface, akin to the role of hydrogen bonds in enzyme catalysts, and the importance of correctly balancing it.