Synthesis, characterization and computational study of CuI nanoparticles immobilized on modified poly (styrene‐co‐maleic anhydride) as a green, efficient and recyclable heterogeneous catalyst in the synthesis of 1,4‐disubstituted 1,2,3‐triazoles via click reaction

Abstract

Poly (styrene‐co‐maleic anhydride) (SMA) was modified by reactionwith4‐amino‐2‐methyl‐10H‐thiene [2,3‐b][1,5]‐benzodiazepine (ATD) hydrochloride, providing an imide with the appropriate sites for the coordination of Cu(I)ions. This modified SMA was reacted with CuI to obtain immobilized Cu(I) NPs. This Cu(I) NPs (CuI/SMI‐TD) was fully characterized by conventional techniques such as FT‐IR, NMR, SEM, TEM, EDAX and ICP‐AES analysis. The SEM and TEM images clearly showed CuI NPs as spherical shapes and the size of particles is 30‐60 nm. Moreover, a quantitative description for experimental features of CuI/SMI‐TD was presented via computational assessment for the interactions between copper metal ions and coordination sites of SMI‐TD ligand. The catalytic activity of this new catalyst was examined in the regioselective synthesis of 1,4‐disubstituted‐1,2,3 triazoles in a classical copper‐catalyzed reaction a so‐called click reaction. The catalyst showed highly efficient catalytic activity, excellent reusability, high yield and more importantly excellent, regioselectivity. The catalyst was recoverable through simple filtration and can be reused at least five times without significant loss of catalytic activity. The heterogeneous nature of the catalyst was confirmed based on the hot filtration test and ICP‐AES analysis.

Computational investigations of click-derived 1,2,3-triazoles as keystone ligands for complexation with transition metals: a review

“…[67][68][69][70][71][72][73][74][75] We also recently focused on combining experimental and computational studies to provide a deeper insight into this important reaction. We reviewed the mechanistical aspects of the 1,3-dipolar Huisgen cycloaddition reactions and the regioselective behavior of metal-catalyzed click reactions using computational chemistry.…”

Preparation of an efficient catalyst through injection of CuI on modified poly (styrene‐co‐maleic anhydride) and theoretical investigation of the structural and electronic properties of catalyst

“…More clearly, we designed an effective model for modified SMI ligand and SMI‐CuI complex with different active nitrogen and oxygen coordinating sites (as were displayed in Scheme ). It should be noted that the proposed structural model for modified SMI polymeric surface can be regarded as an effective model for comparative assessment of metal–ligand interaction strength, with a reliable comprise between accuracy and time saving efficiency of computational process . In this line, we firstly determined the optimized structure of SMI ligand and SMI‐CuI complex model at M08HX/6‐311G** level of theory .…”

Fe3O4@SiO2/EP.EN.EG.Cu as a Highly Efficient and Recoverable Catalytic System for Synthesis of 1,4‐Disubstituted 1,2,3‐Triazole Derivatives via the Click Reaction

“…Besides benzyl halides and substituted epoxides, we also examined alkyl halides in this reaction under the same reaction conditions. 1chlorohexane, 2-bromoethyl benzene, 3-bromo-2-methylprop-1-ene and 1-bromo-2-methylpropan are good substrates to give corresponding 1,4-disubstituted 1,2,3 triazoles in high yiled ( Table 2, entries [15][16][17][18]. However, the whole result show that the cycloaddition reaction phenylacetylene and sodium azide with benzyl halides provided shorter reaction time than alkyl halides.…”

“…Among metal oxide supports, magnetic nanoparticles (Fe 3 O 4 ) offer unique advantages, which include high surface area, adsorptions or immobilization of metals and ligands owing to their very active surface, easy to prepare, and easily separated from the reaction mixture by an external magnet, thus making it a more sustainable catalyst support. [14] Triazoles are a significant class of nitrogen heterocycle compounds in a wide range of applications, such as pharmaceutical, [15] chemical sensors [16] biodegradable, [17] agrochemical agents, [18] corrosion inhibitors. [19] In addition, the application of triazoles as a strong ligand for metal coordination have expanded in recent development coordination chemistry.…”