Copper(II) complex intercalated graphene oxide nanocomposites as versatile, reusable catalysts for click reaction

Abstract

In this work, we report the efficient, high stable copper(II) complexes intercalated graphene oxide (GO) used as green catalysts for copper(II) complex mediated click reaction. Copper(II) Bis(2,2′‐bipyridine) [CuII (bpy)2] (C1) and Copper(II) Bis(1,10‐phenanthroline) [CuII (phen)2] (C2) have synthesized for the intercalation of corresponding nanocomposites with GO, [GO@CuII (bpy)2] (GO‐C1) and [GO@CuII (phen)2] (GO‐C2). The noncovalent interaction of complexes supported on the surface of the GO nanosheets proves as an evident active site to facilitate the enhanced catalytic activity of copper‐catalyzed alkyne azide cycloaddition (CuIIAAC) reaction for the isolation of 1,4‐disubstituted‐1,2,3‐triazoles as click products in shorter reaction time with 80%–91% yield (five examples). The X‐ray diffraction (XRD) pattern of these composites shows the enhanced interlayers d‐spacing range of 1.01–1.12 nm due to the intercalation of copper(II) complexes in between the GO basal planes and characterized by X‐ray photoelectron spectroscopy (XPS), Fourier‐transform infrared spectroscopy (FT‐IR), Raman, UV, scanning electron microscope (SEM), and thermogravimetric analysis (TGA). The as‐prepared nanocomposites were employed for the typical click reactions using the substrates of azide and acetylene. These classes of composite materials can be referred to recyclable, heterogeneous, green catalysts with high atom economy and could also be used for the isolation of click products in biomolecules.

Copper(II)-Bis-Cyclen Intercalated Graphene Oxide as an Efficient Two-Dimensional Nanocomposite Material for Copper-Catalyzed Azide–Alkyne Cycloaddition Reaction

“…Hamed et al have Cu(II)-metformin immobilized on graphene oxide as an efficient and recyclable catalyst for the Beckmann rearrangement (Solaiman Hamed and Mohammad Ali, 2020). In our earlier work, we have reported the highly stable copper(II) complex-intercalated GO nanocomposite as the heterogeneous copper catalyst for the CuAAC reaction and the desired 1,4disubstituted 1,2,3-triazoles were obtained in excellent yield (Samuel et al, 2020). The aim of the present work is to develop a heterogeneous, efficient, nanomaterial catalyst, caging the copper complex over the GO surface for the usage of click reaction in the biological substrates in aqueous medium, upon the reduction of Cu(II) complex-GO composites.…”

Recent Advances in Copper-Based Solid Heterogeneous Catalysts for Azide–Alkyne Cycloaddition Reactions

“…Moreover, Cu@βCD-PEG-mesoGO was recovered and recycled up to ten times without any significant decrease in its activity. More recently, Bhagavathsingh et al [115] reported on the bis(2,2 -bipyridine)copper(II) complex supported on GO (GO@Cu(II)-(bpy) 2 ) for the synthesis of 1,4-disubstituted 1,2,3-triazole derivatives. This catalyst was characterized by an XPS analysis that revealed the presence of copper(I) and copper(II) species in GO@Cu(II)-(bpy) 2 with 3.4% of copper loading, as detected by inductively coupled plasma optical emission spectroscopy (ICP-OES).…”

Carbon–nitrogen bond formation using modified graphene oxide derivatives decorated with copper complexes and nanoparticles

“…Intercalation of copper(II) bis(2,2′‐bipyridine) [Cu(II) (bpy) 2 ] and copper(II) bis(1,10‐phenanthroline) [Cu(II) (phen) 2 ] onto the GO planes [GO@Cu(II) (bpy) 2 ] and [GO@Cu(II) (phen) 2 ] was investigated as a green approach for the preparation of efficient catalysts for “click” reaction. [ 82 ] It should be noted that GO due to its specific features has been integrated in sustainable green chemistry. Van der Waals interactions of bipyridine and phenanthroline ligands of Cu(II) complexes on GO surfaces facilitate the resulting heterogeneous catalyst to provide mass transfer of the organic precursors into desired products in short reaction times.…”