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Structural studies of Schiff-base [2 + 2] macrocycles derived from 2,2′-oxydianiline and the ROP capability of their organoaluminium complexes

Yang, Wenxue; Zhao, Ke-Qing; Prior, Timothy J.; Hughes, David L.; Arbaoui, Abdessamad; Elsegood, Mark R. J.; Redshaw, Carl

Authors

Wenxue Yang

Ke-Qing Zhao

David L. Hughes

Abdessamad Arbaoui

Mark R. J. Elsegood

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



Abstract

The molecular structures of a number of solvates of the [2+2] Schiff-base macrocycles {[2-(OH)-5-(R)-C₆H₂-1,3-(CH)₂][O(2-C₆H₄N)₂]}₂ (R = Me L¹H₂, tBu L²H₂, Cl L³H₂), formed by reacting 2,6-dicarboxy-4-R-phenol with 2,2/-oxydianiline (2-aminophenylether), (2-NH₂C₆H₄)₂O, have been have been determined. Reaction of LnH₂ with two equivalents of AlR/₃ (R/ = Me, Et) afforded dinuclear alkylaluminium complexes [(AlR/₂)₂L1-3] (R = R/ = Me (1), R = tBu, R/ = Me (2), R = Cl, R/ = Me (3), R = Me, R/ = Et (4), R = tBu, R/ = Et (5), R = Cl, R/ = Et (6)). For comparative studies, reactions of two equivalents of AlR/₃ (R/ = Me, Et) with the macrocycle derived from 2,2/-ethylenedianiline and 2,6-dicarboxy-R-phenols (R = Me L⁴H₂, tBu L⁵H₂) were conducted; the complexes [(AlMe)(AlMe2)L⁵]·21/4MeCN (7·21/4MeCN) and [(AlEt₂)₂L⁴] (8) were isolated. Use of limited AlEt₃ with L³H₂ or L⁵H₂ afforded mononuclear bis(macrocyclic) complexes [Al(L³)(L³H)]·4toluene (9·4toluene) and [Al(L⁵)(L⁵H)]·5MeCN (10·5MeCN), respectively. Use of four equivalents of AlR/₃ led to transfer of alkyl groups and isolation of the complexes [(AlR/₂ )₄L1′-3′] (R = L²′, R/ = Me (11); L³′, R/ = Me (12); L¹′, R/ = Et (13); L²′, R/ = Et (14); L³′, R/ = Et (15)), where L1′-3′ is the macrocycle resulting from double alkyl transfer to imine, namely {[2-(O)-5-(R)C₆H₂-1-(CH)-3-(C(R/)H][(O)(2-(N)-2/-C₆H₄N)₂]}₂. Molecular structures of complexes 7·21/4MeCN, 8, 9·4toluene, 10·5MeCN and 11·1¾toluene·11/4hexane are reported. These complexes act as catalysts for the ring opening polymerisation (ROP) of epsilon-caprolactone and rac-lactide; high conversions were achieved over 30 mins at 80 oC for epsilon-caprolactone, and 110 oC over 12 h for rac-lactide.

Citation

Yang, W., Zhao, K., Prior, T. J., Hughes, D. L., Arbaoui, A., Elsegood, M. R. J., & Redshaw, C. (2016). Structural studies of Schiff-base [2 + 2] macrocycles derived from 2,2′-oxydianiline and the ROP capability of their organoaluminium complexes. Dalton transactions : an international journal of inorganic chemistry / RSoC, 45(30), 11990-12005 . https://doi.org/10.1039/c6dt01997h

Journal Article Type Article
Acceptance Date Jun 17, 2016
Online Publication Date Jun 20, 2016
Publication Date Aug 14, 2016
Deposit Date Jun 24, 2016
Publicly Available Date Jun 24, 2016
Journal Dalton transactions
Print ISSN 1477-9226
Electronic ISSN 1477-9234
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 45
Issue 30
Pages 11990-12005
DOI https://doi.org/10.1039/c6dt01997h
Keywords Schiff-base [2+2] macrocycles, 2,2/-oxydianiline , organoaluminium complexes
Public URL https://hull-repository.worktribe.com/output/474191
Publisher URL http://pubs.rsc.org/en/Content/ArticleLanding/2016/DT/C6DT01997H#!divAbstract
Copyright Statement ©2017 University of Hull
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: This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0); : Single-blind; : Received 18 May 2016; Accepted 17 June 2016; Accepted Manuscript published 20 June 2016; Advance Article published 7 July 2016; Version of Record published 26 July 2016

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Copyright Statement
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