Single Fluorine Atom Research Articles

Fluoride Clusterfullerenes: Tuning Metal-Metal Bonding and Magnetic Properties via Single Fluorine Atom Doping.

Endohedral fullerenes are known for their exceptional ability to host metal clusters that contain unique bonding motifs. In this study, we report a facile strategy to synthesize a new family of clusterfullerenes, fluoride clusterfullerenes (FCFs). This work demonstrates that actinides and rare earth metals as well as alkaline earth metals can be encapsulated within a variety of fullerene cages, and these fullerenes can be obtained in their pristine form without additional functionalization methods. Notably, Th2F@Ih(7)-C80 and CaScF@Cs(6)-C82 were isolated and their molecular structures and magnetic properties were characterized by X-ray single-crystal diffraction and multiple spectroscopic techniques as well as DFT calculations. These findings reveal that the unique internal addition of a single fluorine atom significantly alters the metal-metal bonding interactions of Th-Th and Ca-Sc. While Th2@Ih(7)-C80 hosts a σ2 Th-Th bond, an unprecedented actinide-actinide (Th-Th) single electron metal-metal bond is formed inside Th2F@Ih(7)-C80 upon the internal addition of fluoride. Similarly, while a Ca-Sc single electron bond exists in CaSc@Cs(6)-C82, which exhibits excellent molecular qubit properties, the addition of fluoride transforms the compound into a singlet. The present study not only highlights the successful synthesis of a novel family of FCFs, which will likely be an extensive family, it also shows that fluorine doping can induce novel metal-metal bonding motifs leading to potentially intriguing magnetic properties.

Exploring fluorinated heptose phosphate analogues as inhibitors of HldA and HldE, key enzymes in the biosynthesis of lipopolysaccharide

The growing threat of bacterial resistance to antibiotics has led to the rise of anti-virulence strategies as a promising approach. These strategies aim to disarm bacterial pathogens and improve their clearance by the host immune system. Lipopolysaccharide, a key virulence factor in Gram-negative bacteria, has been identified as a potential target for anti-virulence agents. In this study, we focus on inhibiting HldA and HldE, bacterial enzymes from the heptose biosynthesis pathway, which plays a key role in lipopolysaccharide biosynthesis. We present the synthesis of two fluorinated non-hydrolysable heptose phosphate analogues. Additionally, the inhibitory activity of a family of eight heptose phosphate analogues against HldA and HldE was assessed. This evaluation revealed inhibitors with affinities in the low μM range, with the most potent compound showing inhibition constant values of 15.4 μM for HldA and 16.9 μM for HldE. The requirement for a phosphate group at the C-7 position was deemed essential for inhibitory activity, while the presence of a hydroxy anomeric group was found to be beneficial, a phenomenon rationalized through computational modeling. Additionally, the introduction of a single fluorine atom α to the phosphonate moiety conferred a slight advantage for inhibition. These findings suggest that mimicking the structure of d-glycero-β-d-manno-heptose 1,7-bisphosphate, the product of the phosphorylation step in heptose biosynthesis, could be a promising strategy to disrupt this biosynthetic pathway. In terms of the in vivo effects, these heptose phosphate analogues neither demonstrated significant LPS-disrupting effects nor exhibited growth inhibitory activity on their own. Additionally, they did not alter the susceptibility of bacteria to hydrophobic antibiotics. The highly charged nature of these molecules may hinder their ability to penetrate the bacterial cell wall. To overcome this limitation, alternative strategies such as incorporating protecting groups that facilitate their entry and can subsequently be cleaved within the bacterial cytoplasm could be explored.

Fluorine labelling for in situ 19F NMR in oriented systems.

The focus of this project is to take advantage of the large NMR chemical shift anisotropy of 19F to determine the orientation of fluorine labeled biomolecules in situ in oriented biological systems such as muscle. The difficulty with a single fluorine atom is that the orientation determined from a chemical shift is not singlevalued in the case of a fully anisotropic chemical shift tensor. The utility of a labeling approach with two fluorine labels in a fixed molecular framework where one of the labels has an axially symmetric chemical shift anisotropy such as a CF3 group and the other has a fully asymmetric chemical shift anisotropy such as 5-fluorotryptophan is evaluated. The result is that the orientation of the label can be determined straightforwardly from a single one-dimensional 19F NMR spectrum. The potential applications are widespread and not limited to biological applications.

Synthesis and examination of alkoxycyanobiphenyl mesogens with a single fluorine atom at specific locations in the tail

ABSTRACT Selective fluorination is a well-established technique to tailor and improve many of the physical properties of liquid crystals. Cyanobiphenyls are among the best-known and understood thermotropic liquid crystals and have served admirably as a testbed for structural modifications that can eventually be extended to other classes of liquid crystals. As such, and expanding on our earlier work, in the present study of the alkoxycyanobiphenyl M series, the individual tail sites of both 4’-(butoxy)[1,1’-biphenyl]-4-carbonitrile (M12) and 4’-(pentyloxy)[1,1’-biphenyl]-4-carbonitrile (M15) were selectively monofluorinated in order to examine the influence on the phase behavior. These fluorinated compounds were synthesized using epoxidation, regioselective epoxide opening and deoxyfluorination chemistry. In all the fluorinated compounds in both series a monotropic nematic phase was found in the cooling cycle. It was observed that as the fluorine atom on the tail moves closer to the core, the compounds exhibited a metastable room temperature nematic mesophase, but recrystallization invariably occurred. Both enantiomers of 4’-(2-fluorobutoxy)[1,1’-biphenyl]-4-carbonitrile were synthesized in high enantiomeric purity by regioselective opening of chiral epoxide intermediates followed by deoxyfluorination, as established by chiral high-performance liquid chromatography, and their phase behaviors were determined. Moreover, the average dipole moments of the synthesized fluorine substituted derivatives were also calculated.

Chiral Discrimination of Acyclic Secondary Amines by 19F NMR.

Chiral aliphatic amine compounds exhibit a range of physiological activities, making them highly sought-after in the pharmaceutical industry and biological research. One notable obstacle in studying these compounds stems from the pronounced steric hindrance surrounding the nitrogen atom. This characteristic often leads to a weak affinity of acyclic secondary amines for molecular probes, making their chiral discrimination intricate. In response to this challenge, our research has unveiled a novel 19F-labeled probe adept at recognizing and distinguishing between enantiomers of these acyclic secondary amines. By strategically incorporating a single fluorine atom as the 19F label, we have managed to diminish the steric hindrance at the binding site. This alteration bolsters the probe's affinity toward bulkier analytes. As a testament to its effectiveness, we have successfully employed our probe in the chiral analysis of relevant pharmaceuticals, accurately determining their enantiocomposition.

Synthesis of Nucleotides Bearing the 2'-O-Trifluoromethyl Group and Their Application in RNA Analogs Preparation.

The integration of fluorine atoms into biologically active organic compounds has proved to be a vital technique in small molecule drugs. This technique can substantially enhance crucial properties, including metabolic stability, lipophilicity, and bioavailability, often with a mere addition of a single fluorine atom or a trifluoromethyl group. Over the past few decades, this concept has also been applied in nucleic acid chemistry. A commonly employed 2'-OH substitution is the introduction of a 2'-deoxy-2'-fluoro (2'-F) group. The strong electronegativity of fluorine prompts the modified siRNA to readily adopt a C3'-endo conformation, resulting in significant advantages in terms of binding affinity. To enrich the toolbox of chemical modification of oligonucleotides, the replacement of the 2'-OH with the 2'-O-trifluoromethyl group has been developed in RNA analog synthesis. Oligodeoxynucleotides containing the 2'-O-trifluoromethyl group can greatly increase the thermal stability of DNA/RNA duplexes depending on the position and amount of the modification. Moreover, 2'-O-trifluoromethylated oligodeoxynucleotide also exhibited a slightly higher resistance to snake venom phosphodiesterase than the unmodified oligodeoxynucleotide. The 2'-O-trifluoromethylated oligonucleotides can emerge as a label to study RNA structure and function as well, or to develop DNA/RNA-based diagnostics. Hence, it is necessary to report an effective method for the synthesis, deprotection, purification, and characterization of oligonucleotides bearing a 2'-O-trifluoromethyl group. © 2024 Wiley Periodicals LLC. Basic Protocol 1: Preparation of 6-N-benzoyl-5'-O-dimethoxytrityl-2'-O-trifluoromethyl adenosine 3'-(2-cyanoethyl N,N-diisopropyl)phosphoramidite Basic Protocol 2: Preparation of 4-N-acetyl-5'-O-dimethoxytrityl-2'-O-trifluoromethyl cytidine 3'-(2-cyanoethyl N,N-diisopropyl)phosphoramidite Basic Protocol 3: Preparation of 2-N-isobutyryl-5'-O-dimethoxytrityl-2'-O-trifluoromethyl guanine 3'-(2-cyanoethyl N,N-diisopropyl)phosphoramidite Basic Protocol 4: Preparation of 5'-O-dimethoxytrityl-2'-O-2-trifluoromethyl uridine 3'-(2-cyanoethyl N,N-diisopropyl) phosphoramidite Basic Protocol 5: Solid-phase synthesis of 2'-O-trifluoromethylated RNA analogs Basic Protocol 6: Deprotection and purification of 2'-O-trifluoromethyl-RNAs.

Interaction of Aluminum and Platinum Surfaces with the Ionic Liquids 1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide and 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

The processes at the interface between ionic liquids (ILs) and metals are a key factor for understanding especially in electrochemical deposition, nanoscale tribology applications and batteries. In the present work, the interfaces of 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Py1,4]TFSI) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm]TFSI) and platinum and aluminum were investigated by depositing thin IL films and studying them with X-ray photoelectron spectroscopy (XPS) in ultrahigh vacuum. It is found that there is no evidence of a decomposition reaction of either IL on platinum; however, the imidazolium cation of [EMIm]TFSI shows a strong interaction with the surface in the monolayer regime. In contrast, [Py1,4]TFSI and [EMIm]TFSI show massive decomposition on the aluminum surface without applying any electrochemical potential. The spectra for the [TFSI]− anion components show cleavage of C-F or N-S bonds in both cases. Both cleavage of a single fluorine atom and complete cleavage were observed, leading to further decomposition reactions of the anion. Consequently, new components such as AlOOH, Al(OH)3, Al2S3, Al2(SO4)3 and AlF3 appear at the interface. In addition, there is also evidence of decomposition of the cation by the splitting off hydrogen atoms or parts of the alkyl chain in both ILs.

Designer benzodiazepine rat pharmacokinetics: A comparison of alprazolam, flualprazolam and flubromazolam

Designer benzodiazepines, including flualprazolam and flubromazolam, are clandestinely produced to circumvent federal regulations. Although flualprazolam and flubromazolam are structurally similar to alprazolam, they do not have an approved medical indication. Flualprazolam differs from alprazolam by the addition of a single fluorine atom. Whereas, flubromazolam differs by the addition of a single fluorine atom and substitution of a bromine for a chlorine atom. The pharmacokinetics of these designer compounds have not been extensively evaluated. In the present study, we evaluated flualprazolam and flubromazolam in a rat model and compared the pharmacokinetics of both compounds to alprazolam. Twelve male, Sprague-Dawley rats were given a 2 mg/kg subcutaneous dose of alprazolam, flualprazolam and flubromazolam and plasma pharmacokinetic parameters were evaluated. Both compounds displayed significant two-fold increases in volume of distribution and clearance. Additionally, flualprazolam displayed a significant increase in half-life leading to a nearly double half-life when compared to alprazolam. The findings of this study demonstrate that fluorination of the alprazolam pharmacophore increases pharmacokinetic parameters including half-life and volume of distribution. The increase in these parameters for flualprazolam and flubromazolam leads to an overall increased exposure in the body and a potential for greater toxicity than alprazolam.

A Base-Promoted Reductive Coupling Platform for the Divergent Defluorofunctionalization of Trifluoromethylarenes.

We report a trifluoromethylarene reductive coupling method that dramatically expands the scope of difluorobenzylic substructures accessible via C-F bond functionalization. Catalytic quantities of a Lewis base, combined with a disilane reagent in formamide solvent, promotes the replacement of a single trifluoromethyl fluorine atom with a silylated hemiaminal functional group. The reaction proceeds through a difluorobenzyl silane intermediate that can also be isolated. Together, these defluorinated products are shown to provide rapid access to over 20 unique difluoroalkylarene scaffolds.

Donor-Acceptor Boron-Ketoiminate Complexes with Pendent N-Heterocyclic Arms: Switched-on Luminescence through N-Heterocycle Methylation.

A series of intramolecular, donor-stabilized BF2 complexes supported by phenanthridinyl-decorated, β-ketoiminate chelating ligand scaffolds is described, along with their characterization by spectroscopy and X-ray diffraction. In solution, the relative orientation of the pendent phenanthridinyl arm is fixed despite not coordinating to the boron center, and a well-resolved through-space interaction between a phenanthridinyl C-H and a single fluorine atom can be observed by 19F-1H NOE NMR spectroscopy. The neutral compounds are nonetheless only weakly luminescent in fluid solution, ascribed to nonradiative decay pathways enabled by rotation of the N-heterocyclic unit. Methylation of the phenanthridinyl nitrogen restricts this rotation, "switching on" comparably strong emission in solution. Modeling by density functional theory (DFT) and time-dependent DFT (TDDFT) indicates that the character of the lowest energy excitation changes upon methylation, with shallow calculated potential energy surfaces of the neutral complexes consistent with their lack of significant radiative decay.

Structural and Thermal Characterization of Halogenated Azidopyridines: Under-Reported Synthons for Medicinal Chemistry.

Owing to their participation in Click reactions, bifunctional azides are valuable intermediates in the preparation of medicines and biochemical tool compounds. Despite the privileged nature of pyridines among pharmaceutical scaffolds, reports of the synthesis and characterization of azidopyridines bearing a halogen substituent for further elaboration are almost completely unknown in the literature. As azidopyridines carry nearly equal numbers of nitrogen and carbon atoms, we hypothesized that safety concerns limited the application of these useful bifunctional building blocks in medicinal and biological chemistry. To address this concern, we prepared and characterized nine azidopyridines bearing a single fluorine, chlorine, or bromine atom. All were examined by differential scanning calorimetry (DSC), in which they demonstrated exotherms of 228-326 kJ/mol and onset temperatures between 119 and 135 °C. Selected azidopyridines were advanced to mechanical stress testing, in which impact sensitivity was noted for one regioisomer of C5H3FN4. The utility of these versatile intermediates was demonstrated through their use in a variety of Click reactions and the diversification of the halogen handles.

Adsorption of organic molecules on graphene and fluorographene: An unresolved discrepancy between experiment and theory

AbstractHerein, we studied the adsorption of 15 organic and three polar molecules onto pristine and fluorinated graphene. Two levels of fluorination were selected, CF fluorographene for which all carbon atoms are fluorinated and C4F fluorinated graphene, which maximizes the number of Clar sextets. Five different density functionals were employed: M06‐L, M06‐2X, PBE‐D2 and PBE‐D3BJ. In contrast with recent experimental investigations, we found that the adsorption energies for organic molecules onto perfect graphene are significantly lower than those determined for fluorographene. This situation is exacerbated when enthalpic and free energy corrections are included. However, a different scenario was found for polar molecules such as H2O, H2O2 and HF. Partial fluorination following a C4F pattern leads to significantly lower adsorption energies for these three molecules, and the superhydrophilicity of C4F is maintained after thermodynamic corrections are included. In fact, even the removal of a single fluorine atom results in a dramatic change in the adsorption energy of water on fluorographene. We discuss the performance of the density functionals assayed and the importance of using finite and infinite models. This work demonstrates that it is possible to adjust the adsorption energy of a given polar molecule onto graphene by controlling the fluorination level and in doing so, that partially fluorinated graphene models may open new avenues for the separation of molecules with different polarity.

Discovery of BMS-986202: A Clinical Tyk2 Inhibitor that Binds to Tyk2 JH2.

A search for structurally diversified Tyk2 JH2 ligands from 6 (BMS-986165), a pyridazine carboxamide-derived Tyk2 JH2 ligand as a clinical Tyk2 inhibitor currently in late development for the treatment of psoriasis, began with a survey of six-membered heteroaryl groups in place of the N-methyl triazolyl moiety in 6. The X-ray co-crystal structure of an early lead (12) revealed a potential new binding pocket. Exploration of the new pocket resulted in two frontrunners for a clinical candidate. The potential hydrogen bonding interaction with Thr599 in the pocket was achieved with a tertiary amide moiety, confirmed by the X-ray co-crystal structure of 29. When the diversity search was extended to nicotinamides, a single fluorine atom addition was found to significantly enhance the permeability, which directly led to the discovery of 7 (BMS-986202) as a clinical Tyk2 inhibitor that binds to Tyk2 JH2. The preclinical studies of 7, including efficacy studies in mouse models of IL-23-driven acanthosis, anti-CD40-induced colitis, and spontaneous lupus, will also be presented.

Raman and theoretical studies on structural evolution of Li2BeF4 and binary LiF-BeF2 melts

The structural evolution of Li2BeF4 from crystalline to molten states has been investigated by Raman spectroscopic technique with the assist of density functional theory (DFT). The experimental results of temperature-dependent Raman spectra of Li2BeF4 showed that no solid-state phase transformation was taken place during heating process from 298 to 723 K. In the molten state, the structure of BeF42− anion was affected by Li+ cation and environment. For the binary LiF-BeF2 melts with varying LiF/BeF2 ratio, the stretching bands of beryllium‑fluorine bonds in molten Raman spectra were deconvolved identified by Gaussian function. When the concentration of BeF2 exceeding 33 mol%, the dimer Be2F73− was formed and dominated the spectrum. It was characterized to have a linear Be–F–Be geometry with two BeF4 moieties bridged by a single fluorine atom. A second anion Be3F104− processing a triple chain structure formed when the content of BeF2 increasing to 50 mol%. When the concentration of BeF2 went beyond 60 mol%, the Raman intensity and band width gradually decreased. While the intensity and band width of Raman spectra gradually decreased with the concentration of BeF2 exceeding to 60 mol%, which suggests that the band should be assigned to a hexatomic Be6F186− ring which was similar to the situation in the pure BeF2 network structure.

Adsorption-site-dependent magnetic and electronic properties for single- or double-fluorine-atom adsorbed boron nitride nanotubes and their possible applications in spin filters

Here, by using the first-principles method, magnetic and electronic properties of (6, 0) boron nitride nanotubes fluorinated with single fluorine atom (SF-BNNT) or double fluorine atoms (DF-BNNTs) have been investigated. The numerical results show that the non-magnetic and semiconducting BNNT turns to be ferromagnetic and half metallic after a single fluorine atom adsorption. For DF-BNNTs, all the adsorption configurations show ferromagnetic features. However, the electronic properties of DF-BNNTs are closely dependent on adsorption sites of the F adatoms for DF-BNNTs. With different adsorption configurations, DF-BNNTs can be semiconductors, half metals or even conductors. The spin-dependent current-voltage curves of two-probe devices constructed by SF-BNNT or DF-BNNTs indicate that some of the devices manifest high spin filtering efficiency, which can be attributed to the overlap change for the spin-resolved energy bands of two electrodes. This work is helpful for applications of the BNNT in molecular spintronics.

Effect of Fluorine Atom on Photovoltaic Properties of Triphenylamine-Substituted Quinoxaline-Based D-A Type Polymers

A series of two-dimensional triphenylamine (TPA)-substituted quinoxaline-based D-A-type polymers, in which the electron-donating indacenodithiophene unit was linked to the TPA-substituted electron-accepting quinoxaline derivatives, were synthesized. Fluorine, which exhibits a strong electron-withdrawing nature, was systematically incorporated into the structure of the polymers and its effect on the properties of the polymers was investigated. Three target polymers, namely, PIQx-TOF, PIQx-TIF, and PIQx-T2F were synthesized. The Arabic numerals in the names of the polymers indicate the number of fluorine atoms at the 6,7-positions of the triphenylamine-substituted quinoxaline units in the polymers. The structural, optical, and electrochemical characteristics of the polymers were investigated. The PCE of the polymer solar cells with the inverted-type configuration based on the mono-fluorinated polymer, PIQx-TIF, was the highest (5.30%) followed by those of the devices based on PIQx-TOF (4.49%) and the di-fluorinated polymer, PIQx-T2F (4.65%). This enhanced photovoltaic performance of the device with the polymer with a single fluorine atom can be attributed to the increase in the hole mobility, charge generation and dissociation, molecular ordering, and suppression of unfavorable recombination kinetics. Therefore, the incorporation of a single fluorine atom is the optimal condition for the synthesis of TPA-substituted quinoxaline-based polymers for photovoltaic applications.

Polarity effects in 4-fluoro- and 4-(trifluoromethyl)prolines.

Fluorine-containing analogues of proline are valuable tools in engineering and NMR spectroscopic studies of peptides and proteins. Their use relies on the fundamental understanding of the interplay between the substituents and the main chain groups of the amino acid residue. This study aims to showcase the polarity-related effects that arise from the interaction between the functional groups in molecular models. Properties such as conformation, acid–base transition, and amide-bond isomerism were examined for diastereomeric 4-fluoroprolines, 4-(trifluoromethyl)prolines, and 1,1-difluoro-5-azaspiro[2.4]heptane-6-carboxylates. The preferred conformation on the proline ring originated from a preferential axial positioning for a single fluorine atom, and an equatorial positioning for a trifluoromethyl- or a difluoromethylene group. This orientation of the substituents explains the observed trends in the pKa values, lipophilicity, and the kinetics of the amide bond rotation. The study also provides a set of evidences that the transition state of the amide-bond rotation in peptidyl-prolyl favors C4-exo conformation of the pyrrolidine ring.

Organophotoredox Hydrodefluorination of Trifluoromethylarenes with Translational Applicability to Drug Discovery.

Molecular editing such as insertion, deletion, and single atom exchange in highly functionalized compounds is an aspirational goal for all chemists. Here, we disclose a photoredox protocol for the replacement of a single fluorine atom with hydrogen in electron-deficient trifluoromethylarenes including complex drug molecules. A robustness screening experiment shows that this reductive defluorination tolerates a range of functional groups and heterocycles commonly found in bioactive molecules. Preliminary studies allude to a catalytic cycle whereby the excited state of the organophotocatalyst is reductively quenched by the hydrogen atom donor, and returned in its original oxidation state by the trifluoromethylarene.

A Remarkable Difference That One Fluorine Atom Confers on the Mechanisms of Inactivation of Human Ornithine Aminotransferase by Two Cyclohexene Analogues of γ-Aminobutyric Acid.

Human ornithine aminotransferase (hOAT), a pyridoxal 5'-phosphate-dependent enzyme, plays a critical role in the progression of hepatocellular carcinoma (HCC). Pharmacological selective inhibition of hOAT has been shown to be a potential therapeutic approach for HCC. Inspired by the discovery of the nonselective aminotransferase inactivator (1R,3S,4S)-3-amino-4-fluoro cyclopentane-1-carboxylic acid (1), in this work, we rationally designed, synthesized, and evaluated a novel series of fluorine-substituted cyclohexene analogues, thereby identifying 8 and 9 as novel selective hOAT time-dependent inhibitors. Intact protein mass spectrometry and protein crystallography demonstrated 8 and 9 as covalent inhibitors of hOAT, which exhibit two distinct inactivation mechanisms resulting from the difference of a single fluorine atom. Interestingly, they share a similar turnover mechanism, according to the mass spectrometry-based analysis of metabolites and fluoride ion release experiments. Molecular dynamics (MD) simulations and electrostatic potential (ESP) charge calculations were conducted, which elucidated the significant influence of the one-fluorine difference on the corresponding intermediates, leading to two totally different inactivation pathways. The novel addition-aromatization inactivation mechanism for 9 contributes to its significantly enhanced potency, along with excellent selectivity over other aminotransferases.

Light Lanthanide Metallocenium Cations Exhibiting Weak Equatorial Anion Interactions.

As the dysprosocenium complex [Dy(Cpttt)2][B(C6F5)4] (Cpttt=C5H2 tBu3‐1,2,4, 1‐Dy) exhibits magnetic hysteresis at 60 K, similar lanthanide (Ln) complexes have been targeted to provide insights into this remarkable property. We recently reported homologous [Ln(Cpttt)2][B(C6F5)4] (1‐Ln) for all the heavier Ln from Gd–Lu; herein, we extend this motif to the early Ln. We find, for the largest LnIII cations, that contact ion pairs [Ln(Cpttt)2{(C6F5‐κ1‐F)B(C6F5)3}] (1‐Ln; La–Nd) are isolated from reactions of parent [Ln(Cpttt)2(Cl)] (2‐Ln) with [H(SiEt3)2][B(C6F5)4], where the anion binds weakly to the equatorial sites of [Ln(Cpttt)2]+ through a single fluorine atom in the solid state. For smaller SmIII, [Sm(Cpttt)2][B(C6F5)4] (1‐Sm) is isolated, which like heavier 1‐Ln does not exhibit equatorial anion interactions, but the EuIII analogue 1‐Eu could not be synthesised due to the facile reduction of EuIII precursors to EuII products. Thus with the exception of Eu and radioactive Pm this work constitutes a structurally similar family of Ln metallocenium complexes, over 50 years after the [M(Cp)2]+ series was isolated for the 3d metals.