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Iron(III) Complexes for Highly Efficient and Sustainable Ketalization of Glycerol: A Combined Experimental and Theoretical Study

Authors :
Roberto Esposito
Francesco Ruffo
Rossella Di Guida
Maria Elena Cucciolito
Carmen Scamardella
Umberto Raucci
Nadia Rega
Esposito, Roberto
Raucci, Umberto
Cucciolito, Maria E.
Di Guida, Rossella
Scamardella, Carmen
Rega, Nadia
Ruffo, Francesco
Source :
ACS Omega, ACS Omega, Vol 4, Iss 1, Pp 688-698 (2019)
Publication Year :
2018

Abstract

The growing production of biodiesel as a promising alternative and renewable fuel led as the main problem the dramatic increase of its by-product: glycerol. Different strategies for glycerol derivatization have been reported so far, some more efficient or sustainable than others. Herein, we report a very promising and eco-friendly transformation of glycerol in nontoxic solvents and chemicals (i.e., solketal, ketals), proposing three new families of Fe(III) compounds capable of catalysing glycerol acetalization with unpublished turn over frequencies (TOFs), and adhering most of the principles of green chemistry. The comparison between the activity of complexes of formula [FeCl3(1-R)] (1-R = substituted pyridinimine), [FeCl(2-R,R′)] (2-R,R′ = substituted O,O′-deprotonated salens) and their corresponding simple salts reveals that the former are extremely convenient because they are able to promote solketal formation with excellent TOFs, up to 105 h–1. Satisfactory performances were shown with respect to the entire range of substrates, with results being competitive to those reported in the literature so far. Moreover, the experimental activity was supported by an accurate and complete ab initio study, which disclosed the fundamental role of iron(III) as Lewis acid in promoting the catalytic activity. The unprecedented high activity and the low loading of the catalyst, combined with the great availability and the good eco-toxicological profile of iron, foster future applications of this catalytic process for the sustainable transformation of an abundant by-product in a variety of chemicals.

Details

ISSN :
24701343
Volume :
4
Issue :
1
Database :
OpenAIRE
Journal :
ACS omega
Accession number :
edsair.doi.dedup.....c3f6715dc42726af5ebc605a1468d8b2