Skip to main content

Research Repository

Advanced Search

Molybdenum (VI) imido complexes derived from chelating phenols : Synthesis, characterization and ɛ-Caprolactone ROP capability

Al-Khafaji, Yahya; Prior, Timothy; Redshaw, Carl; Elsegood, Mark


Yahya Al-Khafaji

Profile Image

Dr Tim Prior
Senior Lecturer in Inorganic Chemistry

Profile Image

Professor Carl Redshaw
Professor of Inorganic Materials Chemistry and REF Lead for Chemistry

Mark Elsegood


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.


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.

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
Keywords Molybdenum (VI), Imido, Phenolate, Chelate, Crystal structures, ε-caprolactone, Ring opening polymerization
Public URL
Publisher URL
Additional Information This is an open access article published in Catalysts, 2015 v.5 issue 4.


Article.pdf (619 Kb)

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 <br /> (

You might also like

Downloadable Citations