Iron Carbene Complexes Research Articles

Using Iron L-Edge and Nitrogen K-Edge X-ray Absorption Spectroscopy to Improve the Understanding of the Electronic Structure of Iron Carbene Complexes.

Iron-centered N-heterocyclic carbene compounds have attracted much attention in recent years due to their long-lived excited states with charge transfer (CT) character. Understanding the orbital interactions between the metal and ligand orbitals is of great importance for the rational tuning of the transition metal compound properties, e.g., for future photovoltaic and photocatalytic applications. Here, we investigate a series of iron-centered N-heterocyclic carbene complexes with +2, + 3, and +4 oxidation states of the central iron ion using iron L-edge and nitrogen K-edge X-ray absorption spectroscopy (XAS). The experimental Fe L-edge XAS data were simulated and interpreted through restricted-active space (RAS) and multiplet calculations. The experimental N K-edge XAS is simulated and compared with time-dependent density functional theory (TDDFT) calculations. Through the combination of the complementary Fe L-edge and N K-edge XAS, direct probing of the complex interplay of the metal and ligand character orbitals was possible. The σ-donating and π-accepting capabilities of different ligands are compared, evaluated, and discussed. The results show how X-ray spectroscopy, together with advanced modeling, can be a powerful tool for understanding the complex interplay of metal and ligand.

Synthesis and crystal structure of an iron triazole complex resulting from the unexpected ligand cleavage of a triazolium carbene precursor.

Typically reactions of N-heterocyclic carbenes with transition metals are straightforward and require a carbene salt, a base strong enough to deprotonate such a salt and a metal. Yet when carbene precursors are in the form of triazolium salts, reaction may not proceed as easily as expected. In our work, we intended to obtain a triazolylidene complex of iron(II) chloride, but due to the presence of small amounts of water in the tetrahydrofuran solvent used, bis(acetonitrile)tetrakis(1-benzyl-1H-1,2,4-triazole-κN4)iron(II) μ-oxido-bis[trichloridoferrate(III)] acetonitrile disolvate, [Fe(C9H9N3)4(CH3CN)2][Fe2Cl6O]·2CH3CN - an interesting anion with a linear geometry of the O atom - was formed instead of the iron carbene complex. Reaction proceeded via cleavage of the alkyl N-substituent of the triazolium salt. The formation of the product was confirmed by X-ray crystallography. The crystal structure and possible reaction pathways are discussed.

Iron(III) Carbene Complexes with Tunable Excited State Energies for Photoredox and Upconversion.

Substituting precious elements in luminophores and photocatalysts by abundant first-row transition metals remains a significant challenge, and iron continues to be particularly attractive owing to its high natural abundance and low cost. Most iron complexes known to date face severe limitations due to undesirably efficient deactivation of luminescent and photoredox-active excited states. Two new iron(III) complexes with structurally simple chelate ligands enable straightforward tuning of ground and excited state properties, contrasting recent examples, in which chemical modification had a minor impact. Crude samples feature two luminescence bands strongly reminiscent of a recent iron(III) complex, in which this observation was attributed to dual luminescence, but in our case, there is clear-cut evidence that the higher-energy luminescence stems from an impurity and only the red photoluminescence from a doublet ligand-to-metal charge transfer (2LMCT) excited state is genuine. Photoinduced oxidative and reductive electron transfer reactions with methyl viologen and 10-methylphenothiazine occur with nearly diffusion-limited kinetics. Photocatalytic reactions not previously reported for this compound class, in particular the C-H arylation of diazonium salts and the aerobic hydroxylation of boronic acids, were achieved with low-energy red light excitation. Doublet-triplet energy transfer (DTET) from the luminescent 2LMCT state to an anthracene annihilator permits the proof of principle for triplet-triplet annihilation upconversion based on a molecular iron photosensitizer. These findings are relevant for the development of iron complexes featuring photophysical and photochemical properties competitive with noble-metal-based compounds.

Directed C–H activation with iron carbene complexes

The reactivity of PCcarbeneP iron carbenes, was investigated toward imines, ketones, diazenes, 2-vinylpyridine, and 8-methylquinoline, revealing the directed activation of aryl, vinyl, or benzyl C–H bonds by 1,2-addition across the iron-carbene bond.

Stereogenic-at-iron mesoionic carbene complex for enantioselective C-H amidation.

Electronically tuned C 2-symmetric stereogenic-at-iron complexes, featuring strongly σ-donating 1,2,3-triazolin-5-ylidene mesoionic carbene (MIC) ligands, exhibit enhanced catalytic efficiency compared to conventional imidazol-2-ylidene analogs, as demonstrated in nitrene-mediated ring-closing C(sp3)-H amidation reactions. Furthermore, a chiral pinene-derived pyridyl triazole ligand enables a highly diastereoselective synthesis of a non-racemic chiral iron catalyst, thereby controlling the absolute configuration at the metal center, as confirmed by NMR and X-ray crystallography. This pinene-modified stereogenic-at-iron MIC complex demonstrates high catalytic activity and a respectable asymmetric induction in the ring-closing C(sp3)-H amination of N-benzoyloxyurea, yielding 2-imidazolidinones with enantiomeric ratios of up to 92 : 8. These findings reflect the profound potential of this new class of mesoionic carbene iron complexes in further understanding and tuning the reactivity of iron-based catalysts.

Mechanistic and chemoselective investigations on nitrene transfer reactions mediated by a novel iron-mesoionic carbene catalyst

The mesoionic carbene iron complex is a new catalyst, and its catalytic mechanisms for the nitrene transfer reactions were investigated via density functional theory calculations. Especially, the amination-to-aziridination chemoselectivity is predicted for the first time. The origin of the chemoselectivity toward C(sp3)–H amination has been revealed. Based on our calculated results, it can be suggested that the substrate scope of this novel catalytic system may be expanded to alkenes to greatly broaden its potential applications in constructing N-heterocyclic compounds.

Electrochemical polymerisation of newly synthesised 3,4-ethylene dioxythiophene-N-heterocyclic carbene iron complexes and application as redox mediators

Immobilization of redox active complexes as electrodes modifier is appealing for a large set of applications such as sensing, electrolysers or fuel cell. In this work iron based N-heterocyclic carbene complexes bearing an 3,4‑Ethylene dioxythiophene (EDOT) moiety in the side chain have been prepared following two different synthetic approaches determined by the length of the lateral chain. The approaches exploit carbonyldiimidazole (CDI) as the coupling agent between the –CH2OH moiety of the hydroxymethyl-EDOT and the –OH functionalized N-heterocyclic carbene iron complex or the imidazolium salt precursor. In both cases, the syntheses allow to obtain functional monomers suitable for electrochemical polymerization in the form of thin films on conducting substrates. The modified electrodes have been characterized by ATR-IR, showing successful copolymerisation to functionalized poly(3,4‑ethylene dioxythiophene) (PEDOT), by cyclic voltammetry (CV), demonstrating the dominant and reversible redox response of NHC-iron complexes, and by SEM-EDS, which provides the average copolymerisation ratio. The capability of the NHC-iron complex to act as a redox mediator has been assessed by using the functionalized device for glucose detection.

Carbene Transfer from a Pyridine Dipyrrolide Iron–Carbene Complex: Reversible Migration of a Diphenylcarbene Ligand into an Iron–Nitrogen Bond

Carbene Transfer from a Pyridine Dipyrrolide Iron–Carbene Complex: Reversible Migration of a Diphenylcarbene Ligand into an Iron–Nitrogen Bond

Iron-N-heterocyclic carbene complexes as efficient electrocatalysts for water oxidation under acidic conditions.

The development of stable, Earth-abundant, and high-activity molecular water oxidation catalysts under acidic and neutral conditions remains a great challenge. Here, the use of N-heterocyclic carbene (NHC)-based iron(III) complex 1 {[phenyl(tris(3-methylimidazol-1-ylidene))borate]2Fe(III)}+ as a catalyst for water oxidation under acidic and neutral conditions was investigated. Two iron(II) carbene complexes, 2 {[2,6-bis(3-methylimidazolium-1-yl)pyridine]2Fe}2+ and 3 {[2,6-bis(3-methylimidazolium-1-yl)pyridine-4-carboxylic acid]2Fe}2+, were also used for comparison. A series of experiments demonstrate that complex 1 has excellent performance in terms of both catalytic activity and stability. In addition, the faradaic efficiency and turnover frequency (TOF) reach 95.0% and 2.8 s-1, respectively. An overpotential of ca. 490 mV is obtained at pH 1.5. Density functional theory (DFT) calculations indicate that dehydrogenation is the potential-determining step (PDS) in water oxidation. Complex 1 has a lower free energy barrier in this process than 2 and 3. High-valent Fe species are further proven in 1 by spectroelectrochemical measurements, which are crucial in promoting water oxidation. This study is expected to contribute to the development of homogeneous water oxidation catalysis under acidic and neutral conditions.

The first macrocyclic abnormally coordinating tetra-1,2,3-triazole-5-ylidene iron complex: a promising candidate for olefin epoxidation.

The first macrocyclic and abnormally coordinating, mesoionic N-heterocyclic carbene iron complex has been synthesised and characterised via ESI-MS, EA, SC-XRD, CV, NMR and UV/Vis spectroscopy. 13C-NMR spectroscopy and CV measurements indicate a strong σ-donor ability of the carbene moieties, suggesting an efficient catalytic activity of the iron complex in oxidation reactions. Initial tests in the epoxidation of cis-cyclooctene as a model substrate confirm this assumption.

N-Heterocyclic carbene iron complexes catalyze the ring-opening polymerization of lactide.

Poly(lactic acid), PLA, which holds great promise as a biodegradable substitute of fossil resource-derived polyolefins, is industrially produced by the ring-opening polymerization of lactide using a potentially harmful tin catalyst. Based on mechanistic insights into the reaction of N-heterocyclic carbene (NHC) iron complexes with carbonyl substrates, we surmised and demonstrate here that such complexes are excellent catalysts for the bulk polymerization of lactide. We show that an iron complex with a triazolylidene NHC ligand is active at lactide/catalyst ratios of up to 10 000 : 1, produces polylactide with relatively high number-average molecular weights (up to 50 kg mol−1) and relatively narrow dispersity (Đ ∼ 1.6), and features an apparent polymerization rate constant kapp of up to 8.5 × 10−3 s−1, which is more than an order of magnitude higher than that of the industrially used tin catalyst. Kinetic studies and end-group analyses support that the catalytically active species is well defined and that the polymerization proceeds via a coordination–insertion mechanism. The robustness of the catalyst allows technical grade lactide to be polymerized, thus offering ample potential for application on larger scale in an industrially relevant setting.

Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes

Two photoactive iron N-heterocyclic carbene complexes {[hbox {Fe}^{{{rm{II}}}}(hbox {btz})_2(hbox {bpy})]^{2+}} and {[hbox {Fe}^{{rm{III}}}(hbox {btz})_3]^{3+}}, where btz is 3,3’-dimethyl-1,1’-bis(p-tolyl)-4,4’-bis(1,2,3-triazol-5-ylidene) and bpy is 2,2’-bipyridine, have been investigated by Resonant Photoelectron Spectroscopy (RPES). Tuning the incident X-ray photon energy to match core-valence excitations provides a site specific probe of the electronic structure properties and ligand-field interactions, as well as information about the resonantly photo-oxidised final states. Comparing measurements of the Fe centre and the surrounding ligands demonstrate strong mixing of the Fe {hbox {t}_{{rm{2g}}}} levels with occupied ligand pi orbitals but weak mixing with the corresponding unoccupied ligand orbitals. This highlights the importance of pi-accepting and -donating considerations in ligand design strategies for photofunctional iron carbene complexes. Spin-propensity is also observed as a final-state effect in the RPES measurements of the open-shell hbox {Fe}^{{rm{III}}} complex. Vibronic coupling is evident in both complexes, where the energy dispersion hints at a vibrationally hot final state. The results demonstrate the significant impact of the iron oxidation state on the frontier electronic structure and highlights the differences between the emerging class of hbox {Fe}^{{rm{III}}} photosensitizers from those of more traditional hbox {Fe}^{{rm{II}}} complexes.

Probing Redox Non-Innocence in Iron-Carbene Complexes {Fe=C(H)Ar}10-11 by 1,2 H and 13 C Pulse Electron Paramagnetic Resonance.

We report the synthesis and spectroscopic characterization of a series of iron-carbene complexes in redox states {Fe=C(H)Ar}10-11 . Pulse EPR studies of the 1,2 H and 13 C isotopologues of {Fe=C(H)Ar}11 reveal the high covalency of the Fe-carbene bonding, leading to a more even spin distribution than commonly observed for reduced Fischer carbenes.

Probing Redox Non‐Innocence in Iron–Carbene Complexes {Fe=C(H)Ar}10–11by1,2H and13C Pulse Electron Paramagnetic Resonance

AbstractWe report the synthesis and spectroscopic characterization of a series of iron‐carbene complexes in redox states {Fe=C(H)Ar}10–11. Pulse EPR studies of the1,2H and13C isotopologues of {Fe=C(H)Ar}11reveal the high covalency of the Fe–carbene bonding, leading to a more even spin distribution than commonly observed for reduced Fischer carbenes.

N-Heterocyclic Carbene Iron Complexes as Anticancer Agents: In Vitro and In Vivo Biological Studies.

Cisplatin and its derivatives are commonly used in chemotherapeutic treatments of cancer, even though they suffer from many toxic side effects. The problems that emerge from the use of these metal compounds led to the search for new complexes capable to overcome the toxic side effects. Here, we report the evaluation of the antiproliferative activity of Fe(II) cyclopentadienyl complexes bearing n-heterocyclic carbene ligands in tumour cells and their in vivo toxicological profile. The in vitro antiproliferative assays demonstrated that complex Fe1 displays the highest cytotoxic activity both in human colorectal carcinoma cells (HCT116) and ovarian carcinoma cells (A2780) with IC50 values in the low micromolar range. The antiproliferative effect of Fe1 was even higher than cisplatin. Interestingly, Fe1 showed low in vivo toxicity, and in vivo analyses of Fe1 and Fe2 compounds using colorectal HCT116 zebrafish xenograft showed that both reduce the proliferation of human HCT116 colorectal cancer cells in vivo.

High Magnetic Anisotropy of a Square-Planar Iron-Carbene Complex.

Among Earth-abundant catalyst systems, iron-carbene intermediates that perform C-C bond forming reactions such as cyclopropanation of olefins and C-H functionalization via carbene insertion are rare. Detailed descriptions of the possible electronic structures for iron-carbene bonds are imperative to obtain better mechanistic insights and enable rational catalyst design. Here, we report the first square-planar iron-carbene complex (MesPDPPh)Fe(CPh2), where [MesPDPPh]2- is the doubly deprotonated form of [2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine]. The compound was prepared via reaction of the disubstituted diazoalkane N2CPh2 with (MesPDPPh)Fe(thf) and represents a rare example of a structurally characterized, paramagnetic iron-carbene complex. Temperature-dependent magnetic susceptibility measurements and applied-field Mössbauer spectroscopic studies revealed an orbitally near-degenerate S = 1 ground state with large unquenched orbital angular momentum resulting in high magnetic anisotropy. Spin-Hamiltonian analysis indicated that this S = 1 spin system has uniaxial magnetic properties arising from a ground MS = ±1 non-Kramers doublet that is well-separated from the MS = 0 sublevel due to very large axial zero-field splitting (D = -195 cm-1, E/D = 0.02 estimated from magnetic susceptibility data). This remarkable electronic structure gives rise to a very large, positive magnetic hyperfine field of more than +60 T for the 57Fe nucleus along the easy magnetization axis observed by Mössbauer spectroscopy. Computational analysis with complete active space self-consistent field (CASSCF) calculations provides a detailed electronic structure analysis and confirms that (MesPDPPh)Fe(CPh2) exhibits a multiconfigurational ground state. The majority contribution originates from a configuration best described as a singlet carbene coordinated to an intermediate-spin FeII center with a (dxy)2{(dxz),(dz2)}3(dyz)1(dx2-y2)0 configuration featuring near-degenerate dxz and dz2 orbitals.

2+2] Cycloadditions with an Iron Carbene: A Critical Step in Enyne Metathesis.

Ruthenium carbenes, famously used in olefin metathesis, have impacted numerous research areas, ranging from synthesis to materials and biology. Although in the same group as ruthenium, iron carbenes showing similar reaction patterns have not been reported. Such targets are of high interest because the use of a sustainable metal would lead to a decreased cost, toxicity, and environmental impact of the corresponding compounds. Herein, we report the synthesis of an iron carbene complex, [{PC(sp2)P}Fe(N2)(PMe3)] ([PC(sp2)P] = (bis[2-(di-isopropylphosphino)phenyl]methylene), which is capable of performing [2+2] cycloaddition reactions in the presence of alkynes. Specifically, η3-vinyl carbenes are formed stoichiometrically through a [2+2] cycloaddition between the alkyne and the metal carbene. Additional reactivity of the η3-vinyl carbenes with alkynes yields a second insertion product containing a new iron carbene moiety.

Iron-promoted dealkylative carbene aminocyclization of δ-arylamino-α-diazoesters.

Herein, we report a novel methodology to access N-aryl proline derivatives using amino-tethered α-diazoesters and cheap, readily available iron salts. Mechanistically, the aminocyclization reaction involves the initial formation of an iron-carbene complex followed by a nucleophilic attack of the aniline nitrogen atom to give an ammonium ylide intermediate, which finally undergoes the iron-promoted dealkylation.

Photophysics and Photochemistry of Iron Carbene Complexes for Solar Energy Conversion and Photocatalysis

Earth-abundant first row transition metal complexes are important for the development of large-scale photocatalytic and solar energy conversion applications. Coordination compounds based on iron are especially interesting, as iron is the most common transition metal element in the Earth’s crust. Unfortunately, iron-polypyridyl and related traditional iron-based complexes generally suffer from poor excited state properties, including short excited-state lifetimes, that make them unsuitable for most light-driven applications. Iron carbene complexes have emerged in the last decade as a new class of coordination compounds with significantly improved photophysical and photochemical properties, that make them attractive candidates for a range of light-driven applications. Specific aspects of the photophysics and photochemistry of these iron carbenes discussed here include long-lived excited state lifetimes of charge transfer excited states, capabilities to act as photosensitizers in solar energy conversion applications like dye-sensitized solar cells, as well as recent demonstrations of promising progress towards driving photoredox and photocatalytic processes. Complementary advances towards photofunctional systems with both Fe(II) complexes featuring metal-to-ligand charge transfer excited states, and Fe(III) complexes displaying ligand-to-metal charge transfer excited states are discussed. Finally, we outline emerging opportunities to utilize the improved photochemical properties of iron carbenes and related complexes for photovoltaic, photoelectrochemical and photocatalytic applications.

C-H Functionalization via Iron-Catalyzed Carbene-Transfer Reactions.

The direct C-H functionalization reaction is one of the most efficient strategies by which to introduce new functional groups into small organic molecules. Over time, iron complexes have emerged as versatile catalysts for carbine-transfer reactions with diazoalkanes under mild and sustainable reaction conditions. In this review, we discuss the advances that have been made using iron catalysts to perform C-H functionalization reactions with diazoalkanes. We give an overview of early examples employing stoichiometric iron carbene complexes and continue with recent advances in the C-H functionalization of C(sp2)-H and C(sp3)-H bonds, concluding with the latest developments in enzymatic C-H functionalization reactions using iron-heme-containing enzymes.