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Molybdenum complexes derived from the oxydianiline [(2-NH₂C₆H₄)₂O] : synthesis, characterization and ε-caprolactone ROP capability

Elsegood, Mark R.J.; Yang, Wenxue; Zhao, Ke-Qing; Redshaw, Carl; Zhao, Ke Qing; Elsegood, Mark R. J.

Authors

Mark R.J. Elsegood

Wenxue Yang

Ke-Qing Zhao

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

Ke Qing Zhao

Mark R. J. Elsegood



Abstract

The reaction of Na₂MoO₄ with 2,2′-oxydianiline (2-aminophenylether), (2-NH₂C₆H₄)₂O, LH₄, in DME (DME = 1,2-dimethoxyethane) in the presence of Et₃N and Me₃SiCl afforded either the bis(imido) molybdenum(VI) complex {Mo(L)Cl₂(DME)} (1), where L = (2-NC₆H₄)₂O, or the molybdenum(V) salt [Mo(L′)Cl₄][Et₃NH] (2), where L′ = [(2-NH₂C₆H₄)(2-NC₆H₄)O], depending on the work-up method employed. The same diamine reacted with in situ [Mo(NtBu)₂Cl₂(DME)] afforded a tetra-nuclear complex [Mo₄Cl₃(NtBu)₃(OSiMe₃)(μ₄-O)(L)₂(L′)₂]·2MeCN (3·2MeCN). The crystal structures of 1, 2 and 3·2MeCN have been determined. The structure of the bis(imido) complex 1 contains two unique molecules paired up via weak π-stacking, whereas the structure of 2 contains a chelating amine/imido ligand, and is made up of discrete units of two cations and two anions which are interacting via H-bonding. The tetra-nuclear structure 3 contains four different types of distorted octahedral molybdenum centre, and a bent Me₃SiO group thought to originate from the precursor synthesis. Complexes 1–3 have been screened for their ability to ring open polymerize (ROP) ε-caprolactone. For 1 and 3 (not 2), conversion rates were good (>90%) at high temperatures (100 °C) over 6–24 h, and the polymerization proceeded in a living manner.

Citation

Yang, W., Zhao, K., Redshaw, C., & Elsegood, M. R. J. (2015). Molybdenum complexes derived from the oxydianiline [(2-NH₂C₆H₄)₂O] : synthesis, characterization and ε-caprolactone ROP capability. Dalton transactions : an international journal of inorganic chemistry / RSoC, 44(29), 13133-13140. https://doi.org/10.1039/c5dt01799h

Journal Article Type Article
Acceptance Date Jun 11, 2015
Online Publication Date Jun 18, 2015
Publication Date Aug 7, 2015
Deposit Date Jul 17, 2015
Publicly Available Date Jul 17, 2015
Journal Dalton transactions
Print ISSN 1477-9226
Electronic ISSN 1477-9234
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 44
Issue 29
Pages 13133-13140
DOI https://doi.org/10.1039/c5dt01799h
Keywords Molybdenum complexes , 2-NH₂C₆H₄)₂O, ε-caprolactone ROP capability, Ring opening polymerization
Public URL https://hull-repository.worktribe.com/output/376531
Publisher URL http://pubs.rsc.org/en/Content/ArticleLanding/2015/DT/C5DT01799H#!divAbstract
Copyright Statement ©2016 University of Hull
Additional Information Authors' accepted manuscript of article published in: Dalton transactions, 2015, v.44, issue 29 at http://pubs.rsc.org/en/Content/ArticleLanding/2015/DT/C5DT01799H#!divAbstract

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