Scandium Complexes Research Articles

Regenerable and stable olefin-linked covalent organic frameworks with coordination template for selective and efficient trapping of scandium ion

Using coordination templates within covalent organic frameworks (COFs) can significantly enhance the selective properties of these materials. Herein, 1,4-phthalaldehyde, 2,4, 6-trimethyl-1,3, 5-triazine, and a scandium coordination complex were selected to perform a three-in-one strategy, and a class of stable olefin-linked covalent organic frameworks with coordination templates were synthesized. By adjusting the proportion of organic ligands to scandium complexes, a range of crystalline COFs with tunable scandium incorporation levels has been obtained. Upon removing scandium from the material with the suitable metal content, we achieved a metal-imprinted COF (De-Sc-0.33), demonstrating remarkable affinity and selectivity for Sc3+ ions, even in acidic environments and amidst competing metal ions (53.56 mg/g). In particular, the skeleton benefits from the characteristics of olefins, and its regenerability and stability in highly acidic environments surpass those of existing scandium adsorbents (with a capacity drop of less than 2 % after 20 cycles), thus holding tremendous potential for the enrichment of scandium in practical applications.

Assessing the biocompatibility and stability of CeO2 nanoparticle conjugates with azacrowns for use as radiopharmaceuticals.

The application of nanoparticles is promising for the purposes of nuclear medicine due to the possibilities of using them as vectors and transporters of radionuclides. In this study, we have successfully synthesised conjugates of CeO2 nanoparticles and azacrown ligands. Then, the radiolabelling conditions with radionuclides 65Zn, 44Sc and 207Bi were selected and the kinetic stability of the complexes in biologically significant media was evaluated. Optimum conditions for CeO2-APTES-L and CeO2-APTES-DOTA labelling were found: 0.1 g l-1 conjugate and 10-9 M metal cations at 90 °C for complexes with [65Zn]Zn2+, [44Sc]Sc3+ and [207Bi]Bi3+. CeO2-APTES-L-44Sc (radiochemical purity more than 90%) was stable in fetal bovine serum. The obtained results enabled us to choose the most promising complex for biomedical applications for carrying out in vitro and in vivo biodistribution research. Nanoceria and its derivative showed no obvious toxicity to human endothelial cells EA.hy926. Then, the in vivo stability of the studied scandium complex was demonstrated. Taken together, our studies show that functionalised cerium oxide nanoparticles lead to stable radiolabelled nanosystems that may be used for targeted drug delivery, diagnosis and treatment of oncological diseases.

Synthesis and Characterization of Tris(alkoxy) Yttrium and Scandium Complexes Coordinated by Schiff-Base Ligands

Synthesis and Characterization of Tris(alkoxy) Yttrium and Scandium Complexes Coordinated by Schiff-Base Ligands

Binuclear Lantern Complexes of All First-Row 3d Metals Scandium to Zinc: Metal-Metal Bond Lengths and Bond Orders, with Measures of Intrinsic Metal-Metal Bond Strength.

The B3LYP and M06-L functionals with the cc-pVTZ basis set are used to study lantern-type binuclear complexes of all the first-row (3d block) metals scandium to zinc in various low-energy spin states, out of which the ground states are predicted. These complexes are studied as models using mostly the unsubstituted formamidinate ligand. For each metal, metal-metal (MM) bond lengths are related to the formal MM bond orders (zero to five), derived by MO analysis and by electron counting. The predicted ground-state spin multiplicities and MM bond lengths of the model complexes generally agree fairly well with available experimental results on substituted analogues. Finally, values of the formal shortness ratio and Wiberg index for the MM bonds in all of these complexes in all spin states studied are categorized into ranges according to the MM bond orders 0 to 5 in steps of 0.5. The trends shown validate their use in estimating intrinsic metal-metal bond strength regardless of the metal.

Theoretical Studies on the Insertion Reaction of Polar Olefinic Monomers Mediated by a Scandium Complex

This study aimed to investigate the insertion reaction of the polar monomers mediated by the cationic rare earth metal complex [(C5H5)Sc(NMe2CH2C6H4-o)]+ utilizing a combination of density functional theory (DFT) calculations and multivariate linear regression (MLR) methods. The chain initiation step of the insertion reaction could be described by the poisoning effect and the ease of monomer insertion, which could be represented via the DFT-calculated energy difference between σ- and π-coordination complexes (ΔΔE) and insertion energy barrier (ΔG≠), respectively. The results indicate that ΔΔE and ΔG≠ can be predicted by only several descriptors using multiple linear regression methods, with a root mean squared error (RMSE) of less than 2.5 kcal/mol. Furthermore, the qualitative analysis of the MLR models provided effective information on the key factors governing the insertion reaction chain initiation.

Synthesis of Crystallographically Characterizable Bis(cyclopentadienyl) Sc(II) Complexes: (C5H2tBu3)2Sc and {[C5H3(SiMe3)2]2ScI}1.

The synthesis of previously unknown bis(cyclopentadienyl) complexes of the first transition metal, i.e., Sc(II) scandocene complexes, has been investigated using C5H2(tBu)3 (Cpttt), C5Me5 (Cp*), and C5H3(SiMe3)2 (Cp″) ligands. Cpttt2ScI, 1, formed from ScI3 and KCpttt, can be reduced with potassium graphite (KC8) in hexanes to generate dark-red crystals of the first crystallographically characterizable bis(cyclopentadienyl) scandium(II) complex, Cpttt2Sc, 2. Complex 2 has a 170.6° (ring centroid)-Sc-(ring centroid) angle and exhibits an eight-line EPR spectrum characteristic of Sc(II) with Aiso = 82.6 MHz (29.6 G). It sublimes at 200 °C at 10-4 Torr and has a melting point of 268-271 °C. Reductions of Cp*2ScI and Cp″2ScI under analogous conditions in hexanes did not provide new Sc(II) complexes, and reduction of Cp*2ScI in benzene formed the Sc(III) phenyl complex, Cp*2Sc(C6H5), 3, by C-H bond activation. However, in Et2O and toluene, reduction of Cp*2ScI at -78 °C gives a dark-red solution, 4, which displays an eight-line EPR pattern like that of 1, but it did not provide thermally stable crystals. Reduction of Cp″2ScI, in THF or Et2O at -35 °C in the presence of 2.2.2-cryptand, yields the green Sc(II) metallocene iodide complex, [K(crypt)][Cp″2ScI], 5, which was identified by X-ray crystallography and EPR spectroscopy and is thermally unstable. The analogous reaction of Cp*2ScI with KC8 and 18-crown-6 in Et2O gave the ligand redistribution product, [Cp*2Sc(18-crown-6-κ2O,O')][Cp*2ScI2], 6, as the only crystalline product. Density functional theory calculations on the electronic structure of these compounds are reported in addition to a steric analysis using the Guzei method.

Dinitrogen reduction chemistry with scandium provides a complex with two side-on (N[double bond, length as m-dash]N)2- ligands bound to one metal: (C5Me5)Sc[(µ-η2:η2-N2)Sc(C5Me5)2]2.

Although there are few reduced dinitrogen complexes of scandium, this metal has revealed a new structural type in reductive dinitrogen chemistry by reduction of bis(pentamethylcyclopentadienyl) scandium halides under N2. Reduction of (Cp* = C5Me5) with potassium graphite (KC8) under dinitrogen generates the dark blue paramagnetic complex , 1. This end-on bridging (N[double bond, length as m-dash]N)2- complex is a diradical with a magnetic moment of 2.8µ B. Upon further reduction of 1 with KC8, the orange diamagnetic trimetallic complex , 2, is obtained. This complex has an unprecedented structure in which two side-on bridging (N[double bond, length as m-dash]N)2- ligands are bound to the central (Cp*Sc)2+ moiety. Complex 2 can also be obtained directly from reduction of or a mixture of and with KC8. The reaction of with KC8 in the presence of 18-crown-6 or 2.2.2-cryptand affords 2 along with small amounts of , 3, which is green at room temperature and purple at low temperature and displays a mixture of side-on and end-on bridging isomers in the crystal structure collected at -180 °C. Density functional theory (DFT) calculations are consistent with a triplet ground state for the end-on complex 1 and singlet ground states for the side-on complexes 2 and 3.

Copolymerization of tricyclopentadiene and ethylene catalyzed by thiophene-fused-heterocyclic cyclopentadienyl scandium complexes

Tricyclopentadiene–ethylene copolymerization catalysed by scandium complexes and post-hydrogenation of the resultant copolymers with H2 were achieved. The hydrogenated polymers show high glass-transition temperatures and high transparency.

Chiral Discrimination of Monosaccharides Derivatized with 2-Fluorophenyl Hydrazine Using 19F NMR Spectroscopy.

Chiral discrimination of monosaccharides holds significant importance, especially given the growing interest of the pharmaceutical industry in their utilization. However, the majority of existing methods has predominantly centered around chromatographic techniques. In this study, we introduce a 19F NMR-based comprehensive approach for chiral analysis specifically tailored for 15 pairs of aldoses. This technique involves employing sugar hydrazones containing fluorine in combination with chiral octahedral gallium and scandium complexes. By utilizing highly sensitive 19F NMR spectroscopy, the fluorine label in the sugar hydrazone enables accurate differentiation between d and l enantiomers. The efficiency of the newly developed method was demonstrated through its successful application in both quantitative and qualitative analyses of mixtures containing various monosaccharides.

Metal-Ligand Interactions in Scandium Complexes with Radiopharmaceutical Applications.

The radioisotopes of scandium (43Sc, 44Sc, and 47Sc) are potential candidates for use in imaging and therapy both separately and as elementally matched pairs for radiotheranostics. In the present study the bonding interactions of Sc3+ with 18 hepta- to decadentate ligands are compared using density functional theory (DFT) calculations. The bonding analysis is based on the natural bond orbital (NBO) model. The main contributions to the bonding were assessed using natural energy decomposition analysis (NEDA). Most of the ligands have anionic character (charges from 2- to 8-); thus the electrical term determines the major differences in the interaction energies. However, interesting features were found in the covalent contributions manifested by the ligand → Sc3+ charge transfer (CT) interactions. Significant differences could be observed in the energetic contributions of the N and O donors to the total CT.

Scandium-Catalyzed Phenol-Directed Construction of 5-Carbonyl-4-hydroxybenzofurans via Intramolecular Friedel-Crafts Reaction.

Herein we report a scandium-catalyzed regioselective synthesis of 5-carbonyl-4-hydroxybenzofurans via a phenol-directed intramolecular Friedel-Crafts reaction. This synthetic method was applied for the total synthesis of furanoflavones. Experimental studies and density functional theory calculations suggest that hydrogen bond interactions between the phenolic hydroxy group and the scandium complex realize regioselective intramolecular cyclization.

Highly enantioselective hydroxymethylation of unmodified α-substituted aryl ketones in water.

Catalytic asymmetric direct-type aldol reactions of ketones with aldehydes are a perennial puzzle for organic chemists. Notwithstanding the emergence of a myriad of chiral catalysts to address the inherent reversibility of the aldol products, a general method to access acyclic α-chiral ketones from prochiral aryl ketones has remained an unmet synthetic challenge. The approach outlined herein is fundamentally different to that used in conventional catalysis, which typically commences with an α-proton abstraction by a Brønsted base. The use of a chiral 2,2'-bipyridine scandium complex enabled the hydroxymethylation of propiophenone to be run under base-free conditions, which avails effectual suppression of hydrolytic deactivation of the Lewis acid catalyst. Intriguingly, the use of water as a reaction medium had an overriding effect on the progress of the reaction. The sagacious selection of sodium dodecyl sulfate and lithium dodecyl sulfate as surfactants allowed a variety of propiophenone derivatives to react in a highly enantioselective manner.

Towards the MOCVD’s paradise: Thermodynamics of phase transitions of new scandium precursors

Scandium complexes with β-diketonate ligands are valuable precursors for the metal–organic chemical vapour deposition (MOCVD) of scandia based materials. The technology has been constantly developing and demanding novel precursors with accurately defined thermal properties, which could be used in MOCVD as well as related gas phase processes. Two new complexes with 1,1-difluoroacetylacetone (dfac) and 5,5,6,6,6-pentafluorohexane-2,4-dione (5Fac) have been synthesized, isolated, and characterized. The volatility and condensed phase behaviour including thermal stability and phase transitions of the obtained compounds have been studied; the saturated vapour pressures over crystalline Sc(dfac)3 and liquid Sc(5Fac)3 complexes have been measured. As a result, the standard molar thermodynamic characteristics of melting, sublimation, and vaporization processes have been calculated. Thermal properties of these compounds have been compared with literature data on scandium(III) β-diketonates already used as MOCVD precursor. These new compounds can be successfully used as precursors in the gas-phase deposition processes, and the set of obtained thermodynamic data can help in choosing the optimal deposition conditions.

Selective scandium ion capture through coordination templating in a covalent organic framework.

The use of coordination complexes within covalent organic frameworks can significantly diversify the structures and properties of this class of materials. Here we combined coordination chemistry and reticular chemistry by preparing frameworks that consist of a ditopic (p-phenylenediamine) and mixed tritopic moieties-an organic ligand and a scandium coordination complex of similar sizes and geometries, both bearing terminal phenylamine groups. Changing the ratio of organic ligand to scandium complex enabled the preparation of a series of crystalline covalent organic frameworks with tunable levels of scandium incorporation. Removal of scandium from the material with the highest metal content subsequently resulted in a 'metal-imprinted' covalent organic framework that exhibits a high affinity and capacity for Sc3+ ions in acidic environments and in the presence of competing metal ions. In particular, the selectivity of this framework for Sc3+ over common impurity ions such as La3+ and Fe3+ surpasses that of existing scandium adsorbents.

Half-Sandwich Rare-Earth metal complexes bearing 4,5,6,7-Tetrahydroindenyl ligands for highly Syndiospecific (Co)Polymerization of styrene

As Cp-derived ligands, substituted 4,5,6,7-tetrahydroindene (THI) ligands with tunable steric bulk have been synthesized, and their ligated half-sandwich rare-earth metal complexes were also sucessfully prepared and tested for styrene (co)polymerization. In conjunction with [Ph3C][B(C6F5)4], the THI-ligated scandium complexes exhibited high catalytic activity for highly syndiotactic polymerization of styrene (>99% rrrr). THI3Me-Sc/[Ph3C][B(C6F5)4] binary system also promoted the copolymerization of styrene and isoprene/butadiene by both the concurrent addition and sequentical addition of monomers, affording the copolymers with block microstructure as deterimined by NMR (1H and 13C) spectra. The huge difference in reactivity ratios betewen styrene and isoprene/butadiene (rIP / rSt = 31.1 and rBD / rSt = 173.6) revealed in kinetics investigation further proved the predominantly block structure of resultant copolymers.

Proximity-Driven Synergic Copolymerization of Ethylene and Polar Monomers

Coordination copolymerization of ethylene and polar monomers is a promising strategy for preparing structurally well-defined functional polyolefin. However, the poisonous effect of polar groups on employed catalysts is the main obstacle to be overcome. To mimic the synergistic catalysis of multinuclear metal compounds in nature, herein, we report the copolymerization of ethylene with a series of unprotected polar monomers containing oxygen, nitrogen, and sulfur atoms using binuclear half-sandwich scandium complexes C1-Sc2 and C2-Sc2 bearing −CH2– and −CH2CH2– linkers, respectively. In the copolymerization of ethylene and para-methoxystyrene (pMOS), C1-Sc2 and C2-Sc2 exhibit 13 and 7 times greater activities, respectively, than the mononuclear analogue Sc1. For the polar olefins having a butylene spacer, the activities follow the trend C1-Sc2 > C2-Sc2 > Sc1, whereas for the polar olefins that are shorter or longer than the butylene spacer, C2-Sc2 shows the highest activity. Moreover, the synergic effects and the cooperative mechanism for ethylene and pMOS copolymerization with C1-Sc2 were supported by DFT calculations.

Cationic Half-Sandwich Tetrahydrofluorenyl Rare-Earth Metal Complexes as Stable Single-Site Catalysts for (Co)Polymerization of Styrene and Butadiene.

As indenyl-derivates, the tetrahydrofluorenyl ligands had an expanded "wingspan" with considerable steric hindrance. In this text, the rare-earth metal complexes bearing tetrahydrofluorenyl ligands have been synthesized and fully characterized by NMR (1H and 13C) and X-ray diffraction analyses. Upon the activation by [Ph3C][B(C6F5)4], all the scandium complexes exhibited excellent catalytic activity for highly syndioselective polymerization of styrene with a narrow molecular weight distribution (Mw/Mn < 2.0), suggesting the beneficial influence of tetrahydrofluorenyl ligands in stabilizing the single-site active species during the polymerization. Moreover, the scandium-based catalytic systems also promoted the 1,4-regular polymerization of butadiene and its copolymerization with styrene, affording diblock copolymers featuring a highly syndiotactic polystyrene block and a 1,4-specific PBD block. The kinetics investigation revealed the huge gap in TMS-Sc-catalyzed polymerization reactivity ratios (rBD/rSt > 300) between butadiene and styrene, and this further proved the block structure of styrene-butadiene copolymers. The morphology and mechanical property of the selected diblock copolymer were, respectively, investigated by atomic force microscopy and stress-strain experiments.

Metal-Organic Chemical Vapor Deposition Precursors: Diagnostic Check for Volatilization Thermodynamics of Scandium(III) β-Diketonates

Scandium complexes with β-diketonate ligands are valuable precursors for the metal–organic chemical vapor deposition (MOCVD) of scandia based materials, but data on their volatilization thermodynamics crucial to MOCVD technology are in a huge disarray. We have addressed this issue with a diagnostic tool based on the principles of group additivity and structure–property relationships, which had been developed by us specifically for metal–organic objects. For this purpose, a mass of experimental data on the vapor pressures and enthalpies of sublimation, vaporization and fusion available in the literature for scandium(III) β-diketonates has been compiled and analyzed. Additionally, saturated vapor pressures and thermodynamic sublimation characteristics have been obtained for scandium(III) complexes with acetylacetone, hexafluoroacetylacetone, and 3-methyl-2,4-pentanedione by transpiration and thermogravimetric methods. New data have allowed us to arbitrate the conflict of literature data. As a result, a consistent set of enthalpies of the three discussed processes has been obtained for eight scandium complexes. Dispersion interactions and non-additive effects have been shown to be typical for metal tris-β-diketonates. They have been taken into account to improve the diagnostic check. It is now possible to quite easily assess the thermodynamics of tris-β-diketonate complexes with different metals which are in demand as precursors in gas-phase technology.

Terpolymerization of ethylene, norbornene and dicyclopentadiene catalyzed by modified cyclopentadienyl scandium complexes

Terpolymerization of ethylene, norbornene and dicyclopentadiene catalyzed by scandium complexes has been achieved to synthesize corresponding terpolymers. Further transformation results in a huge increase of Tg and decrease in the water contact angle.

Diversified two-electron reduction for trivalent scandium complexes with arene ligands

A series of reduced naphthalene and anthracene complexes of mononuclear scandium were prepared, which undergo diversified two-electron redox reactions with unsaturated molecules.