Highly efficient iron(III) molecular catalysts for solketal production

Esposito, Roberto; Cucciolito, Maria Elena; D’Amora, Angela; Guida, Rossella Di; Montagnaro, Fabio; Ruffo, Francesco

doi:10.1016/j.fuproc.2017.08.018

Cited by 37 publications

(21 citation statements)

References 32 publications

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“…As a proof, a run was performed for isolating solketal. 47 The catalyst loading was kept at 0.00020%, and the product was easily obtained by flash distillation of the excess of acetone with an iron content of less than 10 ppm, and therefore already useful for numerous applications.…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2019

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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solketal, ketals), proposing three new families of Fe(III) compounds capable of catalysing glycerol acetalization with unpublished turn over frequencies (TOFs), and adhering most of the principles of green chemistry.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 [FeCl 3 ( 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 10 5 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.

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Section: Resultsmentioning

confidence: 99%

“…Overall, the ensemble of results returns a clear picture of the “green” features of the process, of actual relevance because a renewable by-product is converted into useful chemicals, and confirms the prominent role played by iron in relevant synthetic processes. 47,73−76…”

Section: Discussionmentioning

confidence: 99%

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

et al. 2019

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“…The best compromise is obtained with complex 1‐Me,Et , which exhibits TOF = 1.4 min –1 and TON = 111. The set of results justifies the increased interest that iron complexes receive in catalysis today, under both homogeneous and heterogeneous conditions.…”

Section: Discussionmentioning

confidence: 56%

Iron(III) Complexes with Cross‐Bridged Cyclams: Synthesis and Use in Alcohol and Water Oxidation Catalysis

et al. 2018

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“…In particular, efficient deep red near IR photoluminescent (DR/NIR PL) emitters are chemically and thermally stable and are easily processable; thus, they are optimal candidates for fluorescence bioimaging and assay applications [13]. Among them, Schiff bases with N , N ′-bis(salicylidene)ethylenediamine (salen) groups and their metal complexes have a wide variety of applications in the fields of biology [14], catalysis [15,16], materials [17], inorganic [2] and analytical chemistry [4].…”

Section: Introductionmentioning

confidence: 99%

The Effect of Bulky Substituents on Two π-Conjugated Mesogenic Fluorophores. Their Organic Polymers and Zinc-Bridged Luminescent Networks

et al. 2019

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From a dicyano-phenylenevinylene (PV) and an azobenzene (AB) skeleton, two new symmetrical salen dyes were obtained. Terminal bulky substituents able to reduce intermolecular interactions and flexible tails to guarantee solubility were added to the fluorogenic cores. Photochemical performances were investigated on the small molecules in solution, as neat crystals and as dopants in polymeric matrixes. High fluorescence quantum yield in the orange-red region was observed for the brightest emissive films (88% yield). The spectra of absorption and fluorescence were predicted by Density Functional Theory (DFT) calculations. The predicted energy levels of the frontier orbitals are in good agreement with voltammetry and molecular spectroscopy measures. Employing the two dyes as dopants of a nematic polymer led to remarkable orange or yellow luminescence, which dramatically decreases in on-off switch mode after liquid crystal (LC) order was lost. The fluorogenic cores were also embedded in organic polymers and self-assembly zinc coordination networks to transfer the emission properties to a macro-system. The final polymers emit from red to yellow both in solution and in the solid state and their photoluminescence (PL) performance are, in some cases, enhanced when compared to the fluorogenic cores.

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Highly efficient iron(III) molecular catalysts for solketal production

Cited by 37 publications

References 32 publications

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

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

Iron(III) Complexes with Cross‐Bridged Cyclams: Synthesis and Use in Alcohol and Water Oxidation Catalysis

The Effect of Bulky Substituents on Two π-Conjugated Mesogenic Fluorophores. Their Organic Polymers and Zinc-Bridged Luminescent Networks

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