Cu RSC Advances - revised.pdf (821.21 kB)
Download file

Mono- and tetra-nuclear copper complexes bearing bis(imino)phenoxide derived ligands: catalytic evaluation for benzene oxidation and ROP of epsilon-caprolactone

Download (821.21 kB)
journal contribution
posted on 07.09.2015, 13:37 authored by Xue Wang, Ke-Qing Zhao, Mark ElsegoodMark Elsegood, Timothy J. Prior, Xiaoming Liu, Li Wu, Sergio Sanz, Euan K. Brechin, Carl Redshaw
Complexes of the type [Cu(L)2] (1) and [Cu4L2(μ4−O)(OAc)4] (2) have been obtained from the reaction of the phenoxydiimine 1,3-(2,6-R22C6H3N=CH)2-5-R1C6H2OH-2 (LH) (where R1 = Me, tBu, Cl; R2 = Me, iPr) with copper(II) acetate [Cu(OAc)2]; changing the molar ratio of the reactants affords 10 differing amounts of 1 or 2. Reaction of the parent dialdehyde [1,3-(CHO)2-5-MeC6H2OH-2] with [Cu(OAc)2] in the presence of Et3N afforded, following work-up, a polymeric chain (3) comprising {[Cu2(OAc)4]OAc}n, HNEt3 and MeCN. The crystal structures of 1 (R1 = Me, R2 = iPr 1a; R1 = Cl, R2 = iPr 1b), 2 (R1 = Me, R2 = Me 2a; R1 = Me, R2 = iPr 2b; R1 = tBu, R2 = Me 2c; R1 = Cl, R2 = Me 2d; R1 = Cl, R2 = iPr 2e; R1 = tBu, R2 =iPr 2f) and 3 are reported (synchrotron radiation was necessary for 3). The 15 magnetic properties of the cluster 2b are presented. Complexes of type 2 and 3 were screened for the ring opening polymerization (ROP) of ε-caprolactone, with or without benzyl alcohol present, under a variety of conditions, however only trace polymer was isolated. The electrochemistry of all complexes was also investigated, together with their ability to catalyze benzene oxidation (using hydrogen peroxide); although low conversions were observed, the tetra-nuclear complexes exhibited excellent selectivity.

Funding

Sichuan Normal University and the National Natural Science Foundation of China (grants 51443004 and 51273133) are thanked for financial support.

History

School

  • Science

Department

  • Chemistry

Published in

RSC ADVANCES

Volume

5

Issue

71

Pages

57414 - 57424 (11)

Citation

WANG, X. ...et al., 2015. Mono- and tetra-nuclear copper complexes bearing bis(imino)phenoxide derived ligands: catalytic evaluation for benzene oxidation and ROP of epsilon-caprolactone. RSC Advances, 5(71), pp.57414-57424.

Publisher

© The Royal Society of Chemistry

Version

AM (Accepted Manuscript)

Publisher statement

This work is made available according to the conditions of the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) licence. Full details of this licence are available at: https://creativecommons.org/licenses/by-nc-nd/4.0/

Publication date

2015

Notes

This paper was accepted for publication in the journal RSC Advances and the definitive published version is available at http://dx.doi.org/10.1039/c5ra08696e

ISSN

2046-2069

Language

en

Usage metrics

Keywords

Exports