scholarly journals Cu(II) and Fe(III) Complexes Derived from N-Acetylpyrazine-2-Carbohydrazide as Efficient Catalysts Towards Neat Microwave Assisted Oxidation of Alcohols

Catalysts ◽  
2019 ◽  
Vol 9 (12) ◽  
pp. 1053 ◽  
Author(s):  
Manas Sutradhar ◽  
Tannistha Roy Barman ◽  
Armando J. L. Pombeiro ◽  
Luísa M. D. R. S. Martins

The mononuclear Cu(II) complex [Cu((kNN′O-HL)(H2O)2] (1) was synthesized using N-acetylpyrazine-2-carbohydrazide (H2L) and characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray crystallography. Two Fe(III) complexes derived from the same ligand viz, mononuclear [Fe((kNN′O-HL)Cl2] (2) and the binuclear [Fe(kNN′O-HL)Cl(μ-OMe)]2 (3) (synthesized as reported earlier), were also used in this study. The catalytic activity of these three complexes (1–3) was examined towards the oxidation of alcohols using tert-butyl hydroperoxide (TBHP) as oxidising agent under solvent-free microwave irradiation conditions. Primary and secondary benzyl alcohols (benzyl alcohol and 1-phenylethanol), and secondary aliphatic alcohols (cyclohexanol) were used as model substrates for this study. A comparison of their catalytic efficiency was performed. Complex 1 exhibited the highest activity in the presence of TEMPO as promoter for the oxidation of 1-phenylethanol with a maximum yield of 91.3% of acetophenone.

2020 ◽  
Vol 21 (8) ◽  
pp. 2832
Author(s):  
Manas Sutradhar ◽  
Tannistha Roy Barman ◽  
Armando J. L. Pombeiro ◽  
Luísa M. D. R. S. Martins

A new hexa-nuclear Cu(II) complex [Cu3(μ2-1κNO2,2κNO2-L)(μ-Cl)2(Cl)(MeOH)(DMF)2]2 (1), where H4L = N′1,N′2-bis(2-hydroxybenzylidene)oxalohydrazide, was synthesized and fully characterized by IR spectroscopy, ESI-MS, elemental analysis, and single crystal X-ray diffraction. Complex 1 and the dinuclear oxidovanadium(V) one [{VO(OEt)(EtOH)}2(1κNO2,2κNO2-L)]·2H2O (2) were used as catalyst precursors for the neat oxidation of primary (cinnamyl alcohol) and secondary (1-phenyl ethanol, benzhydrol) benzyl alcohols and of the secondary aliphatic alcohol cyclohexanol, under microwave irradiation using tert-butyl hydroperoxide (TBHP) as oxidant. Oxidations proceed via radical mechanisms. The copper(II) compound 1 exhibited higher catalytic activity than the vanadium(V) complex 2 for all the tested alcohol substrates. The highest conversion was found for 1-phenylethanol, yielding 95.3% of acetophenone in the presence of 1 and in solvent and promoter-free conditions. This new Cu(II) complex was found to exhibit higher activity under milder reaction conditions than the reported aroylhydrazone Cu(II) analogues.


Molecules ◽  
2018 ◽  
Vol 24 (1) ◽  
pp. 47 ◽  
Author(s):  
Manas Sutradhar ◽  
Tannistha Barman ◽  
Armando Pombeiro ◽  
Luísa Martins

One-dimensional (1D) polynuclear Cu(II) complex (1) derived from (5-bromo-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (H2L) is synthesized and characterized by elemental analysis, IR spectroscopy, ESI-MS, and single crystal X-ray crystallography. Its catalytic performance towards the solvent-free microwave-assisted peroxidative oxidation of aliphatic and aromatic hydrocarbons under mild conditions is compared with that of dinuclear Cu(II) complexes (2 and 3) of the same ligand, previously reported as antiproliferative agents. Polymer 1 exhibits the highest activity, either for the oxidation of cyclohexane (leading to overall yields, based on the alkane, of up to 39% of cyclohexanol and cyclohexanone) or towards the oxidation of toluene (selectively affording benzaldehyde up to a 44% yield), after 2 or 2.5 h of irradiation at 80 or 50 °C, respectively.


Molecules ◽  
2018 ◽  
Vol 23 (10) ◽  
pp. 2699 ◽  
Author(s):  
Manas Sutradhar ◽  
Elisabete Alegria ◽  
M. Guedes da Silva ◽  
Cai-Ming Liu ◽  
Armando Pombeiro

Bis(2-hydroxybenzylidene)isophthalohydrazide (H4L) has been used to synthesize the dinuclear [Cu2(1κNO2:2κN′O′2-H2L)(NO3)2(H2O)2] (1) and the tetranuclear [Cu4(μ-1κNO2:2κN′O2-H2L)2(μ-NO3)2(H2O)4]·2C2H5OH (2) complexes. The solvent plays an important role in determining the ligand behaviour in the syntheses of the complexes. An ethanol-acetonitrile mixture of solvents favours partials enolization in the case of 2. Both complexes have been characterized by elemental analysis, infrared radiation (IR), single crystal X-ray crystallography and electrochemical methods. The variable temperature magnetic susceptibility measurements of 2 show strong antiferromagnetic coupling between the central nitrato-bridged Cu (II) ions. The catalytic activity of both 1 and 2 has been screened toward the solvent-free microwave-assisted oxidation of alcohols and the peroxidative oxidation of alkanes under mild conditions. Complex 1 exhibits the highest activity for both oxidation reactions, leading selectively to a maximum product yield of 99% (for the 1-phenylethanol oxidation after 1 h without any additive) and 13% (for the cyclohexane oxidation to cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone after 3 h).


2020 ◽  
Vol 75 (9-10) ◽  
pp. 851-857
Author(s):  
Chong Chen ◽  
Fule Wu ◽  
Jiao Ji ◽  
Ai-Quan Jia ◽  
Qian-Feng Zhang

AbstractTreatment of [(η6-p-cymene)RuCl2]2 with one equivalent of chlorodiphenylphosphine in tetrahydrofuran at reflux afforded a neutral complex [(η6-p-cymene)RuCl2(κ1-P-PPh2OH)] (1). Similarly, the reaction of [Ru(bpy)2Cl2·2H2O] (bpy = 2,2′-bipyridine) and chlorodiphenylphosphine in methanol gave a cationic complex [Ru(bpy)2Cl(κ1-P-PPh2OCH3)](PF6) (2), while treatment of [RuCl2(PPh3)3] with [2-(C5H4N)CH=N(CH2)2N(CH3)2] (L1) in tetrahydrofuran at room temperature afforded a ruthenium(II) complex [Ru(PPh3)Cl2(κ3-N,N,N-L1)] (3). Interaction of the chloro-bridged complex [Ru(CO)2Cl2]n with one equivalent of [Ph2P(o-C6H4)CH=N(CH2)2N(CH3)2] (L2) led to the isolation of [Ru(CO)Cl2(κ3-P,N,N-L2)] (4). The molecular structures of the ruthenium(II) complexes 1–4 have been determined by single-crystal X-ray crystallography. The properties of the ruthenium(II) complex 4 as a hydrogenation catalyst for acetophenone were also tested.


2010 ◽  
Vol 2010 ◽  
pp. 1-10 ◽  
Author(s):  
Stergios Zanias ◽  
Giannis S. Papaefstathiou ◽  
Catherine P. Raptopoulou ◽  
Konstantinos T. Papazisis ◽  
Vasiliki Vala ◽  
...  

As part of our interest into the bioinorganic chemistry of gallium, gallium(III) complexes of the azole ligands 2,1,3-benzothiadiazole (btd), 1,2,3-benzotriazole (btaH), and 1-methyl-4,5-diphenylimidazole (L) have been isolated. Reaction of btaH or btd withGaBr3orGaCl3resulted in the mononuclear complexes[GaBr3(btaH)2](1) and[GaCl3(btd)2](2), respectively, while treatment ofGaCl3with L resulted in the anionic complex(LH)2[GaCl4](3). All three complexes were characterized by single-crystal X-ray crystallography and IR spectroscopy, while their antiproliferative activities were investigated against a series of human and mouse cancer cell lines.


2018 ◽  
Vol 73 (12) ◽  
pp. 1029-1032
Author(s):  
Peter Mayer ◽  
Hans-Christian Böttcher

AbstractTreatment of THF solutions containing the rhodium(II) complex trans-[RhCl2(PtBu2Ph)2] (1) with [Fe2(CO)9] in the same solvent resulted in the formation of the Vaska-type complex trans-[RhCl(CO)(PtBu2Ph)2] (2) in high yield. The title complex 2 was obtained as pale yellow crystals, characterized by NMR and IR spectroscopy, as well as by microanalyses. Additionally, the molecular structure of 2 has been established by X-ray crystallography. As often reported for similar constituted compounds, the chlorido and carbonyl ligands in crystals of 2 are strongly disordered.


2017 ◽  
Author(s):  
◽  
Sharista Raghunath

The presence of dyes in effluent poses various environmental as well as health hazards for many organisms. Although various remediation strategies have been implemented to reduce their effect, dyes still manage to infiltrate into the environment and hence new strategies are required to address some of the problems. This study investigated the innovation of two cationic water-soluble polymers viz., Proline-Epichlorohydrin-Ethylenediamine Polymer (PEP) and Thiazolidine-Epichlorohydrin-Ethylenediamine Polymer (TEP) that were used to remediate selected synthetic dyes from synthetic effluent by adsorption and dye reduction. Both polymers were synthesized using monomers of a secondary amine, epichlorohydrin and ethylenediamine and were subsequently characterized and modified and their remediation potential studied. In the first study, PEP was synthesized and characterized by 1H-NMR Spectroscopy, FT-IR Spectroscopy, dynamic light scattering, and thermogravimetric analysis (TGA). Thereafter PEP was modified with bentonite clay, by simple mixing of the reactants, to form a Proline-Epichlorohydrin-Ethylenediamine Polymer-bentonite composite (PRO-BEN); it was characterized by FT-IR Spectroscopy, scanning electron microscopy (SEM)/ energy dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Adsorption studies were then undertaken with a synthetic effluent containing three textile dyes, viz., Reactive Blue 222 (RB 222), Reactive Red 195 (RR 195) and Reactive Yellow (RY 145). Various conditions were investigated including pH of the solution, temperature, sodium chloride concentration, initial dye concentration and the dosage of adsorbent used. The experimental data for all dyes followed a Langmuir isotherm. The adsorption process was found to be pseudo-second order. According to the thermodynamic parameters, the adsorption of the dyes was classified as physisorption and the reaction was spontaneous and exothermic. The data were also compared using studies with alumina as an adsorbent. Results showed that PRO-BEN exhibited better absorptivity and desorption than alumina making its use a better recyclable remediation strategy for the removal of organic dyes in wastewater treatment plants. In the second study, TEP was synthesized and then characterized by FT-IR Spectroscopy, 1H-NMR Spectroscopy, TGA and DLS. Thereafter, TEP was used to prepare TEP capped gold nanoparticles (TEP-AuNPs). Herein, two methods were investigated: the Turkevich method and an adaptation of the Turkevich method using bagasse extract. The TEP-AuNPs was characterized by FT-IR Spectroscopy, SEM, EDX, DLS and TEM. Thereafter the reduction of each of Allura Red, Congo Red and Methylene Blue was investigated with the TEP-AuNPs for its catalytic activity toward dye reduction. This study showed that the batch of AuNPs prepared by the Turkevich method had higher rates of dye reduction compared with AuNPs prepared using bagasse extract. Also the quantity of TEP used as capping agent greatly influenced the size, shape and surface charge of the nanoparticles as well as their catalytic performance: the Vroman effect explained this behavior of the TEP-AuNPs. It was finally concluded that whilst PRO-BEN, in the first study, showed excellent dye remediation properties, the second study on TEP-AuNPs showed good catalytic activity for the reduction of selected dyes, however, it was more effective at lower polymer concentration. Finally, both materials displayed good potential for the clean-up of selected synthetic dyes from synthetic effluents.


2013 ◽  
Vol 68 (2) ◽  
pp. 161-167 ◽  
Author(s):  
Muhammad Monim-ul-Mehbooba ◽  
Muhammad Ramzan ◽  
Tobias Rüffe ◽  
Heinrich Lang ◽  
Shafqat Naddem ◽  
...  

A cyanido-bridged Zn(II)-Ag(I) bimetallic coordination polymer, {[Zn(phen)2(H2O){Ag(CN)2}] [Ag(CN)2]·MeOH}n (1), was prepared using ZnCl2, 1,10-phenanthroline (phen) and K[Ag(CN)2] and characterized by IR spectroscopy, thermal analysis and X-ray crystallography. The crystal structure of 1 consists of dinuclear [Zn(phen)2(H2O){Ag(CN)2}]+ cations, [Ag(CN)2]- anions and a methanol molecule. The non-coordinated [Ag(CN)2]- anions are linked to the [Zn(phen)2(H2O){Ag(CN)2}]+ complex cations through argentophilic interactions leading to the formation of chains. The chains are connected by hydrogen bonds and π-π interactions to give a 3D network.


2019 ◽  
Vol 6 (6) ◽  
pp. 780-790 ◽  
Author(s):  
Maciej Barłóg ◽  
Ihor Kulai ◽  
Xiaozhou Ji ◽  
Nattamai Bhuvanesh ◽  
Somnath Dey ◽  
...  

A series of 11 novel fluorinated and non-fluorinated di(thiazolyl)benzenes have been synthesized via microwave assisted Stille coupling and characterized using X-ray crystallography.


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