Metal Salen Research Articles

Transesterification of glycerol with dimethyl carbonate for the synthesis of glycerol carbonate and glycidol by Iron (III) salen complex

The transesterification of glycerol and dimethyl carbonate (DMC) was investigated in the presence of μ-oxo-Fe(salen)2 under the optimal reaction condition. Several transition metal(salen) were tested, and only Fe (salen) shows an excellent results towards transesterification of glycerol. Therefore, Fe (salen) was characterized by IR, elemental analysis, MS, XPS and Surface Basicity test, and it can be confirmed that the as-synthesized Fe(salen) was existed in the form of μ-oxo-Fe(salen)2. It was proposed that the μ-oxo-Fe(salen)2 can provide two different reaction pathway based on its molecular structures and the electronic configuration of iron itself. μ-oxo-Fe(salen)2 was reacted with the mixture of glycerol and DMC under microwave-heating in 60 min at 100°C and at the molar ratio of glycerol:DMC:μ-oxo-Fe(salen)2 of 1:2:0.01 and obtaining the highest glycerol carbonate yield of 93.8 %.

Utility of Immobilized Metal Salens as Electrocatalysts: Fuel Cells and Organic Electrosynthesis

AbstractThere have been significant advancements in the electrosynthesis of fuels and organic molecules, making it an increasingly sustainable and cost‐effective alternative to traditional chemical redox reagents. Early versions of these systems faced challenges in chemoselectivity due to high applied overpotentials, which have been mitigated with the introduction of molecular electrocatalysts, like metal salens (MSalens). These MSalens reduce the required overpotentials, increase turnover numbers (TON), and have simple modularity within their ligand structure allowing for tunable selectivity. While these MSalen electrocatalysts are typically used homogeneously for engineering simplicity, downstream separations are often costly and time‐consuming. Immobilization of MSalens addresses these issues by enabling synthesis at lower potentials, achieving high selectivity, and facilitating straightforward separations. This review explores the application of MSalens in electrosynthesis and immobilized molecular electrocatalysts in organic electrosynthesis.

Synthesis and anion binding properties of (thio)urea functionalized Ni(II)-salen complexes.

Salen ligands (salen = N,N'-ethylenebis(salicylimine)) are well-known for their versatility and widespread utility in chelating metal complexes. However, installation of hydrogen-bonding units on the salen framework, particularly functional groups that require amine-based precursors such as (thio)ureas, is difficult to achieve without the use of protecting group strategies. In this report, we show that the phenylketone analog of salicyladehyde is a stable alternative that enables the facile installation of hydrogen bonding (thio)urea groups on the salen scaffold, thus imparting anion binding abilities to a metal salen complex. Synthesis of symmetric N-phenyl(thio)urea salen ligands functionalized at the 3,3'-position and an unsymmetric salen ligand with N-phenylurea at the 5-position was achieved. Subsequent metalation with nickel(II) acetate afforded the nickel(II) complexes that were investigated for their anion binding properties towards F-, Cl-, Br-, CH3COO-, and H2PO4-. Solid-state structures of the nickel(II) complexes as well as the Cl- bound dimer of the symmetric urea complex were obtained. The unusual acidity of the (thio)urea groups is reflected in the pKa-dependent anion binding behavior of the nickel(II) complexes, as elucidated by 1H and 19F Nuclear Magnetic Resonance (NMR) spectroscopy and Diffusion Ordered Spectroscopy (DOSY) experiments.

Designing Salen‐Based Porous Organic Polymers for Enhanced Electrolytic Water Splitting into Oxygen

AbstractThe development of electricity‐driven oxygen evolution reaction (OER) is a potent solution for energy storage applications. In recent years, there is a surge in interest in designing transition metal‐based catalysts with stable linkages, presenting an efficient alternative to noble metal‐based electrocatalysts. Transition metal complexes linked by salen ligands garner considerable attention due to their capacity to chelate and stabilize metal ions. This work presents a novel approach by strategically incorporating the metal–salen core into a porous organic polymer (POP) backbone, thereby fabricating a highly effective electrocatalyst for oxygen evolution. The judicious selection of metal–salen active sites, coupled with the intramolecular free volume (IMFV) of the triptycene core and the high specific surface area of the salen–POPs, result in superior OER activity. By precisely tuning the structure through variation of the transition metal in the salen unit, deep insights are gained into their electrocatalytic behavior. Notably, the most efficient catalyst, Ni‐DHDA‐TAT, exhibits an impressively low overpotential (η10) of ≈ 270 mV at a current density of 10 mA cm−2 for OER (in 1 m KOH). Further, Ni‐DHDA‐TAT retains its activity even after 50 h of chronoamperometry and 1000 cyclic voltammetry cycles with negligible degradation in its initial performance.

Covalent Bonding of Salen Metal Complexes with Pyrene Chromophores to Porous Polymers for Photocatalytic Hydrogen Evolution.

The development of low-cost and efficient photocatalysts to achieve water splitting to hydrogen (H2) is highly desirable but remains challenging. Herein, we design and synthesize two porous polymers (Co-Salen-P and Fe-Salen-P) by covalent bonding of salen metal complexes and pyrene chromophores for photocatalytic H2 evolution. The catalytic results demonstrate that the two polymers exhibit excellent catalytic performance for H2 generation in the absence of additional noble-metal photosensitizers and cocatalysts. Particularly, the H2 generation rate of Co-Salen-P reaches as high as 542.5 μmol g-1 h-1, which is not only 6 times higher than that of Fe-Salen-P but also higher than a large amount of reported Pt-assisted photocatalytic systems. Systematic studies show that Co-Salen-P displays faster charge separation and transfer efficiencies, thereby accounting for the significantly improved photocatalytic activity. This study provides a facile and efficient way to fabricate high-performance photocatalysts for H2 production.

Catalyst residues severely impact the thermal stability and degradation mechanism of polycarbonates: How to turn a flaw into an opportunity

Three poly(cyclohexene carbonates) with molecular weights ranging from 4.9 to 9.4 kg/mol were synthesized from cyclohexene oxide and CO2 using macrocyclic phenolate dimetallic catalysts and purified by conventional purification procedure. A decrease in thermal stability of approximately 100 °C was observed in comparison to poly(cyclohexene carbonates) with similar molecular weights synthesized using salen metal catalysts. This decrease derives from the presence of traces of dimetallic catalyst which is able to promote the depolymerisation of poly(cyclohexene carbonate) to CO2 and cyclohexene oxide in contrast to the usual backbiting mechanism that leads to cyclic carbonate. The onset of the degradation can be precisely tuned by changing the amount of residual dimetallic catalyst or including species with functional groups that can reduce the availability of the catalytic centers. Therefore, the possibility of controlling the thermal stability of poly(cyclohexene carbonates) by varying the concentration of the catalyst and the surrounding chemical environment paves the way for the use of these polymers as components in self-sacrificial materials of interest for advanced applications.

Atomic and Electronic Structure of Metal–Salen Complexes [M(Salen)], Their Polymers and Composites Based on Them with Carbon Nanostructures: Review of X-ray Spectroscopy Studies

Currently, electrically conductive polymers based on transition metal complexes [M(Salen)], as well as their composites, are among the systems showing promise as catalysts, electrochromic and electroluminescent materials, and electrodes for energy storage (for batteries and supercapacitors). The current review focuses on elucidating the atomic and electronic structure of metal–salen complexes, their polymers, and composites with nanostructured carbon (carbon nanotubes and graphene) using modern X-ray spectroscopy methods (X-ray photoelectron (XPS) and valence-band photoemission (VB PES) spectroscopy, as well as near-edge (NEXAFS) and extended (EXAFS) X-ray absorption fine structure spectroscopy). We trust that this review will be of valuable assistance to researchers working in the field of synthesizing and characterizing metal–salen complexes and composites based on them.

Metal-catalyzed copolymerizations of epoxides and carbon disulfide for high-refractive index low absorbance adhesives and plastics.

High-refractive index plastics are useful materials due to their optical properties, ease of processing, and low-costs compared to their inorganic counterparts. Catalytic carbon disulfide (CS2) copolymerization with epoxides is one method for producing low-cost high refractive index polymers. The reaction is accompanied by an oxygen-sulfur exchange reaction which produces irregular microstructures in the repeating units. In this study, metal salen catalysts were investigated with different metal centers (Al, Cr, Co) and salen ligand electronics, sterics, backbones, and co-catalyst in the copolymerization of CS2 with propylene oxide (PO) and cyclohexene oxide (CHO). The results reveal the essential nature of Cr metal centers on reactivity and the backbone geometry on monomer selectivity. There were no significant impacts on the O-S exchange reaction when ligand design changed, however PO and CHO/CS2 copolymers yield different monothiocarbonate microstructures. Additionally, the effects of microstructure on optical and thermal properties were investigated using spectroscopic ellipsometry and calorimetry, respectively. The CHO system produced high T g plastics (93°C) with high refractive indexes (n up to 1.64), modest absorbance (κ < 0.020), and Abbe numbers of 32.2 while PO yielded low T g adhesives (T g = 9°C) with high refractive indexes (n up to 1.73), low absorbance (κ < 0.005), and low Abbe numbers (V D = 19.1).

Powder crystal structure analysis of salen metal complexes with phenylalkyl groups

Powder crystal structure analysis of salen metal complexes with phenylalkyl groups

Chiral Metal Salen Complexes as Chiral Electrocatalysts for Asymmetric Electrochemical Carboxylation of Acetophenone

AbstractAsymmetric electrochemical carboxylation is the direct and effective method to fix and utilize CO2, and the selection of chiral catalysts is crucial. In this paper, a series of chiral metal salen complexes are prepared as chiral catalysts to achieve enantioselective conversion of acetophenone with CO2 to synthesis chiral 2‐hydroxy‐2‐phenylpropionic acid under electrochemical conditions. Under the catalysis of NiIIL1, the enantiomeric excess (ee) value of 90 % and yield of 59 % are obtained. By cyclic voltammetry and potentiostatic electrolysis, the effects of metal centers and tert‐butyl groups in ligand structures on the catalytic results are studied and the possible reaction mechanism is proposed.

Heterogenization of Salen Metal Molecular Catalysts in Covalent Organic Frameworks for Photocatalytic Hydrogen Evolution

AbstractIntegrating a molecular catalyst with a light harvester into a photocatalyst is an effective strategy for solar light conversion. However, it is challenging to establish a crystallized framework with well‐organized connections that favour charge separation and transfer. Herein, we report the heterogenization of a Salen metal complex molecular catalyst into a rigid covalent organic framework (COF) through covalent linkage with the light‐harvesting unit of pyrene for photocatalytic hydrogen evolution. The chemically conjugated bonds between the two units contribute to fast photogenerated electron transfer and thereby promote the proton reduction reaction. The Salen cobalt‐based COF showed the best hydrogen evolution activity (1378 μmol g−1 h−1), which is superior to the previously reported nonnoble metal based COF photocatalysts. This work provides a strategy to construct atom‐efficient photocatalysts by the heterogenization of molecular catalysts into covalent organic frameworks.

Heterogenization of Salen Metal Molecular Catalysts in Covalent Organic Frameworks for Photocatalytic Hydrogen Evolution.

Integrating a molecular catalyst with a light harvester into a photocatalyst is an effective strategy for solar light conversion. However, it is challenging to establish a crystallized framework with well-organized connections that favour charge separation and transfer. Herein, we report the heterogenization of a Salen metal complex molecular catalyst into a rigid covalent organic framework (COF) through covalent linkage with the light-harvesting unit of pyrene for photocatalytic hydrogen evolution. The chemically conjugated bonds between the two units contribute to fast photogenerated electron transfer and thereby promote the proton reduction reaction. The Salen cobalt-based COF showed the best hydrogen evolution activity (1378 μmol g-1 h-1 ), which is superior to the previously reported nonnoble metal based COF photocatalysts. This work provides a strategy to construct atom-efficient photocatalysts by the heterogenization of molecular catalysts into covalent organic frameworks.

Variation of the Emission Efficiency and Wavelength from Fluorescent Zinc Salen Complexes upon Systematic Structural Modifications.

Understanding the photophysical properties of metal salen complexes is not straightforward because the emission efficiency is altered irregularly upon structural modifications. The present study prepared zinc salen complexes with systematic structural variations to pinpoint critical factors to determine the emission efficiency. One of the important experimental observations is the regiochemistry of a phenolate substituent affecting emission efficiency from a salicylidene fluorophore, which is nicely assigned as arising from the photoexcited electronic structure of metal salen complexes. Another significant finding is the thermal fluctuation of a salen ligand arising from the mismatched ligand-metal interaction, which has a significant impact on fluorescence lifetime. The present study sheds light on hidden factors that alter photophysical properties of a metal salen complex, which provide valuable insights into designing new photoactive salen ligands.

Catalyst Engineering Empowers the Creation of Biomass-Derived Polyesters and Polycarbonates.

The introduction of circular principles in chemical manufacturing will drastically change the way everyday plastics are produced, thereby affecting several aspects of the respective value chains in terms of raw feedstock, recyclability, and cost. The ultimate aim is to ensure a paradigm shift toward plastic-based (consumer) materials that overall can offer a more attractive and sustainable carbon footprint, which is an important requisite from a societal, political, and eventually economical point of view. To realize this important milestone, it is vitally important to control the polymerization processes associated with the creation of novel sustainable materials. In this respect, we realized that expanding the portfolio of biomass-derived monomers may indeed create an impetus for atom circularity; however, the often sterically congested nature of biomass-derived monomers minimizes the ability of previously developed catalysts to activate and transform these precursors. Our motivation was thus spurred by an apparent lack of catalysts suitable for addressing the conversion of such biomonomers, as we realized the potential that new catalytic processes could have to advance and contribute to the development of sustainable materials produced from polycarbonates and polyesters. These two classes of polymers represent crucial ingredients of important and large-scale consumer products and are therefore ideal fits for implementing new catalytic protocols that enable a gradual transition to plastic materials with an improved carbon footprint.When we started our research expedition, the field was dominated by metal catalysts that incorporated preferred, and in some cases even privileged, ligand backbones (such as salens) able to mediate both ring-opening and ring-opening copolymerization manifolds. One major drawback of these aforementioned catalysts is their rather rigid nature, a feature that reduces their ability to act as adaptive systems, especially in cases where bulky monomers are involved. While our initial focus was on the utilization of sustainable metal salen complexes (M = Zn, Fe) for the activation of small cyclic ethers, which are privileged monomers for polyester and polycarbonate production, we were rapidly confronted with severe limitations related to their inability to activate a wider range of complex epoxides and oxetanes, which was imparted by the planar coordination geometry of the salen ligand in most of its applied metal complexes. In our quest to find a catalytically more effective metal complex with the ability to electronically and sterically tune its substrate-binding and substrate-activation potential, we identified aminotriphenolates as structurally versatile, easily accessible, and scalable ligands for various earth-abundant metal cations. Moreover, the ligand backbone allows for switchable coordination environments around the metal centers, thus offering the necessary adaptation in substrate activation events.This Account describes how Al(III)- and Fe(III)-centered aminotriphenolates have conquered a prominent position as catalyst components in the synthesis of new biobased polyester and polycarbonate architectures, thereby changing the landscape of previously difficult to convert biomonomers, and expanding the chemical space of biobased functional polymers. With the ever-increasing influence of legislation and the restrictions placed on the use of fossil-fuel-based feedstock, the polymer industry needs viable alternatives to design materials that are greener, cost-effective, and allow for the exploration and optimization of their recycling and properties.

Controllable synthesis of CO2‐based poly(carbonate‐ether)diols catalyzed by Salen–cobalt complex

AbstractIn our research, the terpolymerization of CO2 and epoxides was realized and the poly(carbonate‐ether)diols were successfully synthesized by the catalysis of Salen–metal complex with the non‐nucleophilic anion, in which the alternated polycarbonate is generally produced. The poly(carbonate‐ether)diols with Mns between 1100 and 8100 g mol−1 and carbonate units (CU) between 31.3% and 52.9% were obtained by tuning temperature, CO2 pressure, time and water addition. Especially the oligo(carbonate‐ether)diols with Mns below 2000 g mol−1 and CU over 40% could be obtained, which were ideal starting materials for polyurethane synthesis and novel CO2‐based polymers with high potential.

Synthesized polyurethane from p‐toluenesulfonyl isocyanate and epichlorohydrin via salen catalysis

AbstractPolyurethane (PU) as a multifunctional material has been produced by various methods. In this work, a series of novel chloric PUs are made from p‐toluene sulfonyl isocyanate (TSI) and epichlorohydrin (ECH) via direct salen catalysis under mild temperature. Catalytic efficiency and activity of salen metal complexes are analyzed and evaluated. The salen‐cobalt (III) (DNP) exhibits high yield, excellent urethane selectivity, narrow polymer weight distribution in bulk polymerization with the molar ratio of TSI with catalyst changing. And compared to bulk polymerization, salen‐cobalt (III) (DNP) can promote the reaction better in solution polymerization and synthesize the product with higher molecular weight. The obtained polymer shows excellent thermal stability, and its thermal degradation starts from 240.8°C. So, it will provide experience for developing functional PU under mild reaction conditions.

Efficient Recovery of Noble Metal Ions (Pd2+, Ag+, Pt2+, and Au3+) from Aqueous Solutions Using N,N'-Bis(salicylidene)ethylenediamine (Salen) as an Extractant (Classic Solvent Extraction) and Carrier (Polymer Membranes).

This paper presents the results of the first application of N,N'-bis(salicylidene)ethylenediamine (salen) as an extractant in classical liquid–liquid extraction and as a carrier in membrane processes designed for the recovery of noble metal ions (Pd2+, Ag+, Pt2+, and Au3+) from aqueous solutions. In the case of the utilization of membranes, both sorption and desorption were investigated. Salen has not been used so far in the sorption processes of precious metal ions. Recovery experiments were performed on single-component solutions (containing only one type of metal ions) and polymetallic solutions (containing ions of all four metals). The stability constants of the obtained complexes were determined spectrophotometrically. In contrast, electrospray ionization high-resolution mass spectrometry (ESI-HRMS) was applied to examine the elemental composition and charge of the generated complexes of chosen noble metal ions and salen molecules. The results show the great potential of N,N'-bis(salicylidene)ethylenediamine as both an extractant and a carrier. In the case of single-component solutions, the extraction percentage was over 99% for all noble metal ions (molar ratio M:L of 1:1), and in the case of a polymetallic solution, it was the lowest, but over 94% for platinum ions and the highest value (over 99%) for gold ions. The percentages of sorption (%Rs) of metal ions from single-component solutions using polymer membranes containing N,N'-bis(salicylidene)ethylenediamine as a carrier were highest after 24 h of the process (93.23% for silver(I) ions, 74.99% for gold(III) ions, 69.11% and 66.13% for palladium(II) and platinum(II) ions, respectively), similar to the values obtained for the membrane process conducted in multi-metal solutions (92.96%, 84.26%, 80.94%, and 48.36% for Pd(II), Au(III), Ag(I), and Pt(II) ions, respectively). The percentage of desorption (%Rdes) was very high for single-component solutions (the highest, i.e., 99%, for palladium solution and the lowest, i.e., 88%, for silver solution), while for polymetallic solutions, these values were slightly lower (for Pt(II), it was the lowest at 63.25%).

Self-Assembled Bimetallic Aluminum-Salen Catalyst for the Cyclic Carbonates Synthesis.

Bimetallic bis-urea functionalized salen-aluminum catalysts have been developed for cyclic carbonate synthesis from epoxides and CO2. The urea moiety provides a bimetallic scaffold through hydrogen bonding, which expedites the cyclic carbonate formation reaction under mild reaction conditions. The turnover frequency (TOF) of the bis-urea salen Al catalyst is three times higher than that of a μ-oxo-bridged catalyst, and 13 times higher than that of a monomeric salen aluminum catalyst. The bimetallic reaction pathway is suggested based on urea additive studies and kinetic studies. Additionally, the X-ray crystal structure of a bis-urea salen Ni complex supports the self-assembly of the bis-urea salen metal complex through hydrogen bonding.

Modification of Ti-doped Hematite Photoanode with Quasi-molecular Cocatalyst: A Comparison of Improvement Mechanism Between Non-noble and Noble Metals.

Loading of molecular catalyst on the surface of semiconductors is an attractive way to boost the water oxidation activity. As active sites, molecular water oxidation cocatalysts show increasing attraction and application possibility. In order to compare the advantages between molecular catalysts with non-noble and noble metals, the loading of the Fe(salen) and Ru(salen) as cocatalyst precursors on the surface of Ti-Fe2 O3 was investigated Quasi-Fe(salen) and Ru(salen) improved the photocurrent density by 1.5 and 1.7 times compared to that of the original Ti-Fe2 O3 photoanode, respectively. The quasi-Fe(salen) could improve the conductivity and reaction kinetics on the photoanode surface. By contrast, the notable advancements could be attributed to more reaction sites for quasi-Ru(salen) as cocatalysts. Thus, non-noble quasi-Fe(salen) is a promising cocatalyst to replace the noble metal salen, and further optimization can be expected with regard to the precise control of reaction sites.

Theoretical design of Salen–metal-based materials for highly selective separation of C2H2/C2H4

C2H4 is an essential industrial organic chemical. Efficiently removing C2H2 from C2H2/C2H4 mixtures is a significant challenge. Introducing a Salen–metal unit into porous materials is a practical way to separate gas mixtures. In this work, we used density functional theory (DFT) and grand canonical Monte Carlo (GCMC) method investigated the performances of different Salen–metal complexes in separating C2H2 from C2H4. The gas adsorption energies of fourteen Salen–metal complexes were systemically studied. Two complexes, Salen–Mn (II) and Salen–Ni (II), exhibited superior adsorptive selectivity in capturing C2H2 and C2H4. This result will be helpful for developing porous materials for the efficient removal of C2H2 from C2H2/C2H4 mixtures.