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Title: Manganese coordination chemistry of bis(imino)phenoxide derived [2 + 2] Schiff-base macrocyclic ligands
Authors: Yang, Wenxue
Zhao, Ke-Qing
Wang, Bi-Qin
Redshaw, Carl
Elsegood, Mark R.J.
Zhao, Jiang-Lin
Yamato, Takehiko
Keywords: Macrocyclic ligands
Transition metals
Crystal structures
Issue Date: 2016
Publisher: © Royal Society of Chemistry
Citation: YANG, W. ... et al., 2016. Manganese coordination chemistry of bis(imino)phenoxide derived [2 + 2] Schiff-base macrocyclic ligands. Dalton Transactions, 45 (1), pp.226-236.
Abstract: The [2 + 2] Schiff-base macrocycles [2,2’-(CH2CH2)(C6H4NvCH)2-2,6-(4-RC6H2OH)]2 (IRH2), upon reaction with MnCl2 (two equivalents) afforded the bimetallic complex [Cl3Mn(μ-Cl)Mn(IMeH2)] (1) or the salt complex [Cl3Mn(NCMe)][MnCl(ItBuH2)] (2). Under similar conditions, use of the related [2 + 2] oxy-bridged macrocycle [2,2’-O(C6H4NvCH)2-4-RC6H2OH] (IIRH2), afforded the bimetallic complexes [(MnCl)2IIR] (R = Me 3, tBu 4), whilst the macrocycle derived from 1,2-diaminobenzene and 5,5’-di-tert-butyl-2,2’-dihydroxy-3,3’-methylenedibenzaldehyde (IIIH4) afforded the complex [(MnCl)2(III)]·2MeCN (5·2MeCN). For comparative studies, the salt complexes [2,6-(ArNHCH)2-4-MeC6H2O][MnCl3(NCMe)] (Ar = 2,4-Me2C6H3, 6) and {[(2-ArNvCH),6-(ArNHCH)-4-Me-C6H2O]MnCl}2[MnCl4]·8CH2Cl2 (Ar = 4-MeC6H4, 7·8CH2Cl2) were prepared. The crystal structures of 1–7 are reported (synchrotron radiation was necessary for complexes 1, 3 and 5). Complexes 1–7 (not 5) were screened for their potential to act as pre-catalysts for the ring opening polymerization (ROP) of e-caprolactone; 3, 4 and 6, 7 were inactive, whilst 1 and 2 exhibited only poor activity with low conversion (<15%) at temperatures above 60 °C.
Sponsor: We thank Sichuan Normal University and the National Natural Science Foundation of China (Grants 51443004 and 51273133) for financial support. The Special Funds for sharing large precision equipment (No. DJ2014-22) at Sichuan Normal University is also thanked. The EPSRC is thanked for a travel award (EP/L012804/1) to CR.
Version: Accepted for publication
DOI: 10.1039/c5dt03453a
URI: https://dspace.lboro.ac.uk/2134/21105
Publisher Link: http://dx.doi.org/10.1039/c5dt03453a
ISSN: 1477-9226
Appears in Collections:Closed Access (Chemistry)

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