Yahya Al-Khafaji
Molybdenum (VI) imido complexes derived from chelating phenols : Synthesis, characterization and ɛ-Caprolactone ROP capability
Al-Khafaji, Yahya; Prior, Timothy; Redshaw, Carl; Elsegood, Mark
Authors
Dr Tim Prior T.Prior@hull.ac.uk
Senior Lecturer in Inorganic Chemistry
Professor Carl Redshaw C.Redshaw@hull.ac.uk
Professor of Inorganic Materials Chemistry and REF Lead for Chemistry
Mark Elsegood
Abstract
Reaction of the bulky bi-phenols 2,2′-RCH[4,6-(t-Bu)₂C₆H₂OH]₂ (R = Me L¹ᵐᵉH₂, Ph L¹ᵖʰH₂) with the bis(imido) molybdenum(VI) tert-butoxides [Mo(NR¹)(NR²)(Ot-Bu)₂] (R¹ = R² = 2,6-C₆H₃-i-Pr₂; R¹ = t-Bu, R² = C₆F₅) afforded, following the successive removal of tert-butanol, the complexes [Mo(NC₆H₃ᵢ-Pr₂-2,6)₂L¹ᵐᵉ] (1), [Mo(NC₆H₃i-Pr₂-2,6)₂L¹ᵖʰ] (2) and [Mo(Nt-Bu)(μ-NC₆F₅)(L¹ᵐᵉ)]₂ (3). Similar use of the tri-phenol 2,6-bis(3,5-di-tert-butyl-2-hydroxybenzyl)-4-methylphenol (L²H₃) with [Mo(NC₆H₃ᵢ-Pr₂-2,6)₂(Ot-Bu)₂] afforded the oxo-bridged product [Mo(NC₆H₃i-Pr₂-2,6)(NCMe)(μ-O)L2H]₂ (4), whilst use of the tetra-phenols α,α,α′,α′-tetrakis(3,5-di-tert-butyl-2-hydroxyphenyl)-p- or -m-xylene L³ᵖH₄/L³ᵐH₄ led to {[Mo(NC₆H₃ᵢ-Pr₂-2,6)₂]₂(μ-L³ᵖ)} (5) or {[Mo(NC₆H₃ᵢ-Pr₂-2,6)₂]₂(μ-L³ᵐ)} (6), respectively. Similar use of [Mo(NC₆F₅)₂(Ot-Bu)₂] with L³ᵖH₄ afforded, after work-up, the complex {[Mo(NC₆F₅)(Ot-Bu)₂]₂(μ-L³ᵖ)}·6MeCN (7·6MeCN). Molecular structures of 1, 2·CH₂Cl₂, 3, 4·6MeCN, 6·2C₆H₁₄, and 7·6MeCN are reported and these complexes have been screened for their ability to ring open polymerize (ROP) ε-caprolactone; for comparative studies the precursor complex [Mo(NC₆H₃ᵢ-Pr₂-2,6)₂Cl₂(DME)] (DME = 1,2-dimethoxyethane) has also been screened. Results revealed that good activity is only achievable at temperatures of ≥100 °C over periods of 1 h or more. Polymer polydispersities were narrow, but observed molecular weights (Mn) were much lower than calculated values.
Citation
Al-Khafaji, Y., Prior, T., Redshaw, C., & Elsegood, M. (2015). Molybdenum (VI) imido complexes derived from chelating phenols : Synthesis, characterization and ɛ-Caprolactone ROP capability. Catalysts, 5(4), 1928-1947. https://doi.org/10.3390/catal5041928
Journal Article Type | Article |
---|---|
Acceptance Date | Nov 2, 2015 |
Online Publication Date | Nov 12, 2015 |
Publication Date | Nov 12, 2015 |
Deposit Date | Dec 10, 2015 |
Publicly Available Date | Nov 23, 2017 |
Journal | Catalysts |
Electronic ISSN | 2073-4344 |
Publisher | MDPI |
Peer Reviewed | Peer Reviewed |
Volume | 5 |
Issue | 4 |
Pages | 1928-1947 |
DOI | https://doi.org/10.3390/catal5041928 |
Keywords | Molybdenum (VI), Imido, Phenolate, Chelate, Crystal structures, ε-caprolactone, Ring opening polymerization |
Public URL | https://hull-repository.worktribe.com/output/382394 |
Publisher URL | http://www.mdpi.com/2073-4344/5/4/1928 |
Additional Information | This is an open access article published in Catalysts, 2015 v.5 issue 4. |
Contract Date | Nov 23, 2017 |
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Copyright Statement
© 2015 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license
(http://creativecommons.org/licenses/by/4.0/)
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