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

Wang, Xue; Zhao, Ke-Qing; Elsegood, Mark R. J.; Prior, Timothy J.; Liu, Xiaoming; Wu, Li; Sanz, Sergio; Brechin, Euan K.; Redshaw, Carl

Authors

Xue Wang

Ke-Qing Zhao

Mark R. J. Elsegood

Xiaoming Liu

Li Wu

Sergio Sanz

Euan K. Brechin

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Professor Carl Redshaw C.Redshaw@hull.ac.uk
Professor of Inorganic Materials Chemistry and REF Lead for Chemistry



Abstract

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-R¹ C₆H₂OH-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 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 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.

Citation

Wang, X., Zhao, K., Elsegood, M. R. J., Prior, T. J., Liu, X., Wu, L., …Redshaw, C. (2015). Mono- and tetra-nuclear copper complexes bearing bis(imino)phenoxide derived ligands: catalytic evaluation for benzene oxidation and ROP of ε-caprolactone. RSC advances, 5(71), 57414-57424. https://doi.org/10.1039/c5ra08696e

Journal Article Type Article
Acceptance Date Jun 8, 2015
Online Publication Date Jun 8, 2015
Publication Date Jan 1, 2015
Deposit Date Jul 22, 2015
Publicly Available Date Jul 22, 2015
Journal RSC advances
Print ISSN 2046-2069
Electronic ISSN 2046-2069
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 5
Issue 71
Pages 57414-57424
DOI https://doi.org/10.1039/c5ra08696e
Keywords Ring opening polymerization , Bis(imino)phenoxide derived ligands, ε-caprolactone, Benzene oxidation
Public URL https://hull-repository.worktribe.com/output/376772
Publisher URL http://pubs.rsc.org/en/Content/ArticleLanding/2015/RA/C5RA08696E#!divAbstract
Additional Information : This document is Similarity Check deposited; : Supplementary Information; : Crystal Structure Data; : The Royal Society of Chemistry has an exclusive publication licence for this journal; OPEN ACCESS: The accepted version of this article will be made freely available after a 12 month embargo period; : Single-blind; : Received 10 May 2015; Accepted 8 June 2015; Accepted Manuscript published 8 June 2015; Version of Record published 1 July 2015

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