Microwave-assisted one-pot functionalization of metal–organic framework MIL-53(Al)-NH2 with copper(II) complexes and its application in olefin oxidation

T. Bunchuay; R. Ketkaew; P. Chotmongkolsap; T. Chutimasakul; J. Kanarat; Y. Tantirungrotechai; J. Tantirungrotechai

doi:10.1039/C7CY01941F

Microwave-assisted one-pot functionalization of metal–organic framework MIL-53(Al)-NH₂ with copper(ii) complexes and its application in olefin oxidation

T. Bunchuay,

^a R. Ketkaew,^b P. Chotmongkolsap,^ac T. Chutimasakul,^a J. Kanarat,^a Y. Tantirungrotechai^b and J. Tantirungrotechai

*^ac

Author affiliations

* Corresponding authors

^a Center for Catalysis Science and Technology, Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400, Thailand
E-mail: jonggol.jar@mahidol.ac.th, jonggol@gmail.com

^b Computational Chemistry Research Unit, Department of Chemistry, Faculty of Science and Technology, Thammasat University, Pathum Thani 12120, Thailand

^c Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400, Thailand

Abstract

A simple, rapid, and efficient functionalization of the metal–organic framework MIL-53(Al)-NH₂ with copper(II) complexes by microwave irradiation is described. The one-pot post-synthetic modification was based on the Schiff base reaction between the aldehyde added and the primary aryl amino group in the organic linker of MIL-53(Al)-NH₂, which afforded coordination sites for copper(II). The effects of synthetic parameters such as solvent, reaction time, and reactant ratio were evaluated. The functionalized materials were structurally characterized and examined for potential applications in catalysis. The copper complex functionalized MIL-53(Al) was active towards the oxidation of olefins with tert-butyl hydroperoxide as an oxidant. The results showed that if the olefin possessed allylic hydrogens such as cyclohexene, allylic oxidation products were obtained, but epoxide was the major product obtained from terminal olefins without allylic hydrogens. The reaction mechanism based on density functional theory calculations provides some insights into the observed experimental results.

Article information

https://doi.org/10.1039/C7CY01941F

Article type

Paper

Submitted

21 Sep 2017

Accepted

10 Nov 2017

First published

13 Nov 2017

Download Citation

Catal. Sci. Technol., 2017,7, 6069-6079

Permissions

Request permissions

Microwave-assisted one-pot functionalization of metal–organic framework MIL-53(Al)-NH₂ with copper(II) complexes and its application in olefin oxidation

T. Bunchuay, R. Ketkaew, P. Chotmongkolsap, T. Chutimasakul, J. Kanarat, Y. Tantirungrotechai and J. Tantirungrotechai, Catal. Sci. Technol., 2017, 7, 6069 DOI: 10.1039/C7CY01941F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Catalysis Science & Technology