Stable Fe(iii) phenoxyimines as selective and robust CO2 /epoxide coupling catalysts

Dalton Transactions : an International Journal of Inorganic Chemistry
Eszter FazekasJennifer A Garden

Abstract

Three phenoxyimine Fe(iii)Cl complexes bearing electronically diverse -Cl, -H or -tBu substituents in the ortho position were synthesised. X-ray crystallographic analysis of the complexes reveals mononuclear structures with pentacoordinate iron centres and trigonal bipyramidal geometries. All three complexes demonstrated excellent catalytic activities towards CO2/epoxide coupling to selectively form cyclic carbonates, with catalyst activity correlating with the electron withdrawing nature of the ortho-substituent (Cl > H > tBu) and thus the Lewis acidity of the metal centre. The chloro-substituted complex displayed remarkable activity in the synthesis of propylene carbonate from propylene oxide and CO2, reaching turnover frequencies (TOF) up to 760 h-1 in the presence of TBABr co-catalyst at 120 °C and 20 bars of CO2 pressure. Importantly, the catalyst is also very robust, functioning with high substrate loading, under air or in the presence of water. The substrate scope was successfully extended to other terminal epoxides including epichlorohydrin (TOF = 900 h-1) and to the more challenging internal epoxide, cyclohexene oxide (TOF = 80 h-1). These are amongst the highest TOF values reported for an iron CO2/epoxide coupling cat...Continue Reading

References

Sep 9, 2004·Chemical Society Reviews·Pier Giorgio Cozzi
Feb 18, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Jan M BeckerPeter Scott
Mar 30, 2010·Chemical Reviews·Benjamin SchäffnerArmin Börner
Sep 28, 2010·Chemical Communications : Chem Comm·Antoine BuchardCharlotte K Williams
Feb 22, 2012·Acta Crystallographica. Section E, Structure Reports Online·Roghayieh JamjahBehrouz Notash
Nov 10, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Heeralal Vignesh Babu, Krishnamurthi Muralidharan
Jan 11, 2013·Journal of the American Chemical Society·Christopher J WhiteoakArjan W Kleij
Feb 14, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·M A FuchsM Döring
Mar 21, 2013·Chemistry : a European Journal·Fernando Castro-GómezCarles Bo
Jul 25, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Punnamchandar RamidiAnindya Ghosh
Aug 29, 2013·Chemical Reviews·Hua ZhangJian-Min Yue
Jan 22, 2014·Chemistry : a European Journal·Christopher J WhiteoakArjan W Kleij
Apr 15, 2014·Chemical Communications : Chem Comm·Jie QinYingming Yao
Jun 29, 2014·Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy·Mojtaba AminiL Keith Woo
Jan 9, 2015·Acta Crystallographica. Section C, Structural Chemistry·George M Sheldrick
Jan 9, 2016·Chemistry : a European Journal·José A Castro-OsmaXiao Wu
Jun 2, 2016·Chemistry : a European Journal·Lanka D WickramasingheCláudio N Verani
Apr 26, 2017·Topics in Current Chemistry·Hendrik BüttnerThomas Werner
May 1, 2016·Chemical Science·Kailong ZhuStephen P Thomas

❮ Previous
Next ❯

Citations

Sep 14, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Oliver J DriscollMatthew D Jones
May 22, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Tamilarasan AjaykamalMallayan Palaniandavar
May 22, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Sethuraman MuthuramalingamRamasamy Mayilmurugan
Sep 20, 2019·Inorganic Chemistry·Sethuraman MuthuramalingamRamasamy Mayilmurugan

❮ Previous
Next ❯

Methods Mentioned

BETA
X-ray

Software Mentioned

SHELXT
Diamond
Olex2
SHELXS
SHELXL

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.