1-Tetralone, a useful synthetic intermediate in the manufacture of pharmaceuticals, agrochemicals and dyes, can be prepared by liquid phase catalytic oxidation of tetralin. Selective oxidation of tetralin to 1-tetralo...1-Tetralone, a useful synthetic intermediate in the manufacture of pharmaceuticals, agrochemicals and dyes, can be prepared by liquid phase catalytic oxidation of tetralin. Selective oxidation of tetralin to 1-tetralone is still a big challenge with low-temperature processes using environmentally friendly routes even after decades of research. Herein, we demonstrate room-temperature oxidation of tetralin to 1-tetralone over layered double hydroxide-hosted sulphonato-salen-nickel(II) complex, LDH-[Ni-salen]. The layered double hydroxide-hosted sulphonato-salen-nickel(II) compound was characterized by powder X-ray diffraction, Fourier transform infrared spectrometer (FTIR), UV-Visible diffuse reflectance spectra, scanning electron microscopy (SEM) and elemental analysis. The theoretical calculations of free sulphonato-salen-nickel(II) complex using Density Functional Theory/CAM-B3LYP at the 6-311++ G(d,p) level of theory were also used to determine the orientation of the Ni-salen compound within the layered structure. The immobilized compound, LDH-[Ni-salen] was found to be an effective reusable catalyst for the oxidation of tetralin to 1-tetralone using a combination of trimethylacetaldehyde and molecular oxygen (14.5 psi) and at 25°C. At 45.5% conversion, tetralin was converted to 1-tetralone with 77.2% selectivity at room temperature and atmospheric pressure after 24 h. The catalyst recycles test and hot filtration experiment showed that oxidation proceeded through Ni(II) sites in LDH-[Ni-salen]. The catalysts were reused several times without losing their catalytic activity and selectivity. The present results may provide a convenient strategy for the preparation of 1-tetralone using layered double hydroxide-based heterogeneous catalyst at ambient temperature for industrial application in near future.展开更多
The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in ab...The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in absence of photosensitizers. Herein, we report the systematic study of the interaction between the oxidized form bqdi ligand, tris-(o-benzoquinonediimine) with divalent first-row transition metal series using DFT calculations. The lowest energy structures, bond length, binding energies, frontier molecular orbital analysis, natural bond orbitals, and global reactivity descriptor were calculated using B3LYP/6-311G(d,P) level of theory. The time dependent-DFT at the CAM-B3LYP/6-311+G(d,p) level of theory was applied to determine the electronic structures and the optical spectra. The theoretical binding trend of the divalent first-row transition metal series is decreasing as follows: Cu >Ti > V > Co > Ni > Fe > Cr > Zn >Mn. Among them, the binding potency of iron (II) by the bqdi ligand was not predominantly sturdy as compared to other first-row divalent transition metal ions. The origin of strong coordination with Fe(II) is attributed to its extra capability to induce covalent coordination of bqdi ligands. The complex exhibited two strong peaks at 370 nm and 452 nm, due to the HOMO-3 to LUMO+1 and HOMO-1 to LUMO transitions, respectively. Natural bond orbital analysis showed that the major interaction happens between the N lone pair electrons of the ligand with an anti-bonding orbital of metal ions, in which Ti showed the highest interaction energy than other metal ions. The present systemic DFT study of bqdi ligands with the first-row transition metals strongly encourages the future establishment of photochemical hydrogen production in absence of photosensitizers.展开更多
Liquid phase catalytic hydroxylation of phenol by Fe-containing metal-organic framework, Fe-BTC (BTC = 1,3,5-benzenetricarboxylate) using 30% H2O2 as an oxidant and H2O as solvent showed good activity and stability un...Liquid phase catalytic hydroxylation of phenol by Fe-containing metal-organic framework, Fe-BTC (BTC = 1,3,5-benzenetricarboxylate) using 30% H2O2 as an oxidant and H2O as solvent showed good activity and stability under mild reaction conditions. Phenol reacts with hydrogen peroxide over Fe-BTC to produce two main products, viz., catechol and hydroquinone. The effect of temperature, time, substrate/hydrogen peroxide mole ratio and amount of catalyst on catalytic performance were studied. The catalyst could be reused four times without losing significant loss of catalytic performance. The crystallinity and structure of catalyst were unchanged during the catalysis reaction, as confirmed by comparison of XRD and SEM of the fresh and reused catalyst. A reaction mechanism is proposed based on the experimental results.展开更多
As a substitute for lithium ion batteries, Na chemistry for ion battery systems is promising materials for energy storage applications for the next generation. Herein, the structures, IR and UV-visible spectra of 2-am...As a substitute for lithium ion batteries, Na chemistry for ion battery systems is promising materials for energy storage applications for the next generation. Herein, the structures, IR and UV-visible spectra of 2-aminoterephthalic acid (H2ATA), disodium 2-aminoterephthalate (Na2ATA), trisodium 2-aminotere-phthalate (Na3ATA) and tetrasodium 2-aminoterephthalate (Na4ATA) have been studied using density functional theory (DFT/B3LYP/6-311++G(d,p)). The theoretical geometric parameters and FTIR results showed very good agreement with the experimental results. Different conformers of Na2ATA, Na3ATA and Na4ATA showed that the binding energy per sodium in Na2ATA, Na3ATA and Na4ATA is -694.94, -543.44 and -407.46 kJ/mol, respectively. The Na3ATA and Na4ATA salts are higher in energy (151.46 and 287.48 kJ/mol, respectively) than Na2ATA, indicating the higher stability of the Na2ATA complex. The calculated binding energy, enthalpy and Gibbs free energy of Na2ATA, Na3ATA and Na4ATA revealed that the compounds are thermodynamically stable. Natural bond orbital (NBO) analysis of Na2ATA, Na3ATA and Na4ATA indicated that the major interaction occurs between the lone pair electrons of the oxygen atom and anti-bonding orbitals of carbon atoms of the two carboxylate ions. UV-visible spectrum of the free H2ATA and its sodium salts Na2ATA, Na3ATA and Na4ATA were performed using the time-dependent density functional theory (TD-DFT) method at the level of B3LYP/6-311++G(d,p). The frontier molecular orbital energetic parameters and global reactivity descriptors revealed that the Na4ATA and Na3ATA complexes exhibited a higher band gap (ΔEgap) and electronegativity (χeV) than Na2ATA.展开更多
文摘1-Tetralone, a useful synthetic intermediate in the manufacture of pharmaceuticals, agrochemicals and dyes, can be prepared by liquid phase catalytic oxidation of tetralin. Selective oxidation of tetralin to 1-tetralone is still a big challenge with low-temperature processes using environmentally friendly routes even after decades of research. Herein, we demonstrate room-temperature oxidation of tetralin to 1-tetralone over layered double hydroxide-hosted sulphonato-salen-nickel(II) complex, LDH-[Ni-salen]. The layered double hydroxide-hosted sulphonato-salen-nickel(II) compound was characterized by powder X-ray diffraction, Fourier transform infrared spectrometer (FTIR), UV-Visible diffuse reflectance spectra, scanning electron microscopy (SEM) and elemental analysis. The theoretical calculations of free sulphonato-salen-nickel(II) complex using Density Functional Theory/CAM-B3LYP at the 6-311++ G(d,p) level of theory were also used to determine the orientation of the Ni-salen compound within the layered structure. The immobilized compound, LDH-[Ni-salen] was found to be an effective reusable catalyst for the oxidation of tetralin to 1-tetralone using a combination of trimethylacetaldehyde and molecular oxygen (14.5 psi) and at 25°C. At 45.5% conversion, tetralin was converted to 1-tetralone with 77.2% selectivity at room temperature and atmospheric pressure after 24 h. The catalyst recycles test and hot filtration experiment showed that oxidation proceeded through Ni(II) sites in LDH-[Ni-salen]. The catalysts were reused several times without losing their catalytic activity and selectivity. The present results may provide a convenient strategy for the preparation of 1-tetralone using layered double hydroxide-based heterogeneous catalyst at ambient temperature for industrial application in near future.
文摘The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in absence of photosensitizers. Herein, we report the systematic study of the interaction between the oxidized form bqdi ligand, tris-(o-benzoquinonediimine) with divalent first-row transition metal series using DFT calculations. The lowest energy structures, bond length, binding energies, frontier molecular orbital analysis, natural bond orbitals, and global reactivity descriptor were calculated using B3LYP/6-311G(d,P) level of theory. The time dependent-DFT at the CAM-B3LYP/6-311+G(d,p) level of theory was applied to determine the electronic structures and the optical spectra. The theoretical binding trend of the divalent first-row transition metal series is decreasing as follows: Cu >Ti > V > Co > Ni > Fe > Cr > Zn >Mn. Among them, the binding potency of iron (II) by the bqdi ligand was not predominantly sturdy as compared to other first-row divalent transition metal ions. The origin of strong coordination with Fe(II) is attributed to its extra capability to induce covalent coordination of bqdi ligands. The complex exhibited two strong peaks at 370 nm and 452 nm, due to the HOMO-3 to LUMO+1 and HOMO-1 to LUMO transitions, respectively. Natural bond orbital analysis showed that the major interaction happens between the N lone pair electrons of the ligand with an anti-bonding orbital of metal ions, in which Ti showed the highest interaction energy than other metal ions. The present systemic DFT study of bqdi ligands with the first-row transition metals strongly encourages the future establishment of photochemical hydrogen production in absence of photosensitizers.
文摘Liquid phase catalytic hydroxylation of phenol by Fe-containing metal-organic framework, Fe-BTC (BTC = 1,3,5-benzenetricarboxylate) using 30% H2O2 as an oxidant and H2O as solvent showed good activity and stability under mild reaction conditions. Phenol reacts with hydrogen peroxide over Fe-BTC to produce two main products, viz., catechol and hydroquinone. The effect of temperature, time, substrate/hydrogen peroxide mole ratio and amount of catalyst on catalytic performance were studied. The catalyst could be reused four times without losing significant loss of catalytic performance. The crystallinity and structure of catalyst were unchanged during the catalysis reaction, as confirmed by comparison of XRD and SEM of the fresh and reused catalyst. A reaction mechanism is proposed based on the experimental results.
文摘As a substitute for lithium ion batteries, Na chemistry for ion battery systems is promising materials for energy storage applications for the next generation. Herein, the structures, IR and UV-visible spectra of 2-aminoterephthalic acid (H2ATA), disodium 2-aminoterephthalate (Na2ATA), trisodium 2-aminotere-phthalate (Na3ATA) and tetrasodium 2-aminoterephthalate (Na4ATA) have been studied using density functional theory (DFT/B3LYP/6-311++G(d,p)). The theoretical geometric parameters and FTIR results showed very good agreement with the experimental results. Different conformers of Na2ATA, Na3ATA and Na4ATA showed that the binding energy per sodium in Na2ATA, Na3ATA and Na4ATA is -694.94, -543.44 and -407.46 kJ/mol, respectively. The Na3ATA and Na4ATA salts are higher in energy (151.46 and 287.48 kJ/mol, respectively) than Na2ATA, indicating the higher stability of the Na2ATA complex. The calculated binding energy, enthalpy and Gibbs free energy of Na2ATA, Na3ATA and Na4ATA revealed that the compounds are thermodynamically stable. Natural bond orbital (NBO) analysis of Na2ATA, Na3ATA and Na4ATA indicated that the major interaction occurs between the lone pair electrons of the oxygen atom and anti-bonding orbitals of carbon atoms of the two carboxylate ions. UV-visible spectrum of the free H2ATA and its sodium salts Na2ATA, Na3ATA and Na4ATA were performed using the time-dependent density functional theory (TD-DFT) method at the level of B3LYP/6-311++G(d,p). The frontier molecular orbital energetic parameters and global reactivity descriptors revealed that the Na4ATA and Na3ATA complexes exhibited a higher band gap (ΔEgap) and electronegativity (χeV) than Na2ATA.
