Special Issue "Recent Developments on Catalysis by Metalloporphyrins and Analogues"

A special issue of Catalysts (ISSN 2073-4344).

Deadline for manuscript submissions: 31 July 2020.

Special Issue Editors

Dr. Mário Manuel Quialheiro Simões
Website
Guest Editor
Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
Interests: organic chemistry; sustainable chemistry; oxidation; metalloporphyrins; catalysis; homogeneous catalysis; heterogeneous catalysis
Dr. Susana Luísa Henriques Rebelo
Website
Guest Editor
Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Campo Alegre Street, 4169-007 Porto, Portugal
Interests: metalloporphyrins; catalysis; oxidation; green chemistry; hydrogen peroxide; materials science; mechanisms

Special Issue Information

Dear Colleagues,

The synthetic versatility and the potential applications of metalloporphyrins in several fields, including catalysis, have catapulted the interest of researchers in these complexes, all over the world, particularly trying to mimic biological systems, such as cytochrome P450 enzymes. In the last few decades, significant developments on catalytic processes based on synthetic metalloporphyrins have been registered, mostly devoted to, although not exclusively to, oxidative transformations. In addition to hydroxylation, epoxidation or sulfoxidation reactions, other metalloporphyrins’ catalyzed transformations are playing an important role, such as reduction, halogenations or carbene transfer reactions, including significant developments on asymmetric catalysis. Meanwhile, several metalloporphyrin analogues are also playing a major role in catalysis.

We would like to invite authors to submit regular research papers, communications, and short reviews to this Special Issue, which aims to cover the most recent advances in the field of catalysis mediated by metalloporphyrins and analogues in either homogeneous and heterogeneous conditions, including asymmetric catalytic systems.

Dr. Mário Manuel Quialheiro Simões
Dr. Susana Luísa Henriques Rebelo
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1800 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Porphyrins
  • Corroles
  • Phthalocyanines
  • Catalysis
  • Biomimetic catalysis
  • Homogeneous catalysis
  • Heterogeneous catalysis

Published Papers (7 papers)

Order results
Result details
Select all
Export citation of selected articles as:

Research

Open AccessArticle
Covalent Functionalization of Nanodiamonds by Ruthenium Porphyrin, and Their Catalytic Activity in the Cyclopropanation Reaction of Olefins
Catalysts 2020, 10(6), 666; https://doi.org/10.3390/catal10060666 - 13 Jun 2020
Abstract
Detonation nanodiamonds (DNDs) were functionalized by ruthenium porphyrins and used as catalysts in the cyclopropanation reaction of olefins. The heterogeneous catalyst was characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and XPS (X-ray photoelectron spectroscopy). The XPS was used to control [...] Read more.
Detonation nanodiamonds (DNDs) were functionalized by ruthenium porphyrins and used as catalysts in the cyclopropanation reaction of olefins. The heterogeneous catalyst was characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and XPS (X-ray photoelectron spectroscopy). The XPS was used to control the binding of the ruthenium porphyrin to the DNDs’ surface. This catalyst was used in the cyclopropanation reactions of simple olefins and was reused with no loss of activity in four consecutive cycles, after recovering each time by simple centrifugation. Full article
(This article belongs to the Special Issue Recent Developments on Catalysis by Metalloporphyrins and Analogues)
Show Figures

Graphical abstract

Open AccessArticle
A Kinetic Study on the Efficient Formation of High-Valent Mn(TPPS)-oxo Complexes by Various Oxidants
Catalysts 2020, 10(6), 610; https://doi.org/10.3390/catal10060610 - 01 Jun 2020
Abstract
New, more efficient methods of wastewater treatment, which will limit the harmful effects of textile dyes on the natural environment, are still being sought. Significant research work suggests that catalysts based on transition metal complexes can be used in efficient and environmentally friendly [...] Read more.
New, more efficient methods of wastewater treatment, which will limit the harmful effects of textile dyes on the natural environment, are still being sought. Significant research work suggests that catalysts based on transition metal complexes can be used in efficient and environmentally friendly processes. In this context, a number of compounds containing manganese have been investigated. A suitable catalyst should have the capacity to activate a selected oxidant or group of oxidants, in order to be used in industrial oxidation reactions. In the present study we investigated the ability of MnIII(TPPS), where TPPS = 5,10,15,20-tetrakis(4-sulphonatophenyl)-21H,23H-porphyrine, to activate five different oxidants, namely hydrogen peroxide, peracetic acid, sodium hypochlorite, potassium peroxomonosulfate and sodium perborate, via the formation of high valent Mn(TPPS)-oxo complexes. Kinetic and spectroscopic data showed that the oxidation process is highly pH dependent and is strongly accelerated by the presence of carbonate in the reaction mixture for three of the five oxidizing agents. The highest efficiency for the oxidation of MnIII(TPPS) to high-valent Mn(TPPS)-oxo complexes, was found for peracetic acid at pH ≈ 11 in 0.5 M carbonate solution, which is at least an order of magnitude higher than the rate constants found for the other tested oxidants under similar conditions. Full article
(This article belongs to the Special Issue Recent Developments on Catalysis by Metalloporphyrins and Analogues)
Show Figures

Graphical abstract

Open AccessArticle
Theoretical Study on Electronic Structural Properties of Catalytically Reactive Metalloporphyrin Intermediates
Catalysts 2020, 10(2), 224; https://doi.org/10.3390/catal10020224 - 13 Feb 2020
Cited by 1
Abstract
Metalloporphyrins have attracted great attention in the potential application of biomimetic catalysis. Especially, they were widely investigated as green catalysts in the chemical oxidation of various hydrocarbons through the catalytic activation of molecular oxygen. The structural properties of active central metal ions were [...] Read more.
Metalloporphyrins have attracted great attention in the potential application of biomimetic catalysis. Especially, they were widely investigated as green catalysts in the chemical oxidation of various hydrocarbons through the catalytic activation of molecular oxygen. The structural properties of active central metal ions were reported to play a decisive role in catalytic activity. However, those delicate structural changes are difficult to be experimentally captured or elucidated in detail. Herein, we explored the electronic structural properties of metalloporphyrins (metal porphyrin (PMII, PMIIICl)) and their corresponding catalytically active intermediates (metal(III)-peroxo(PMIII-O2), metal(III)-hydroperoxo(PMIII-OH), and metal(IV)-oxo(PMIV=O), (M=Fe, Mn, and Co)) through the density functional theory method. The ground states of these intermediates were determined based on the assessment of relative energy and the corresponding geometric structures of ground states also further confirmed the stability of energy. Furthermore, our analyses of Mulliken charges and frontier molecular orbitals revealed the potential catalytic behavior of reactive metalloporphyrin intermediates. Full article
(This article belongs to the Special Issue Recent Developments on Catalysis by Metalloporphyrins and Analogues)
Show Figures

Figure 1

Open AccessArticle
Biomimetic Oxidation of Benzofurans with Hydrogen Peroxide Catalyzed by Mn(III) Porphyrins
Catalysts 2020, 10(1), 62; https://doi.org/10.3390/catal10010062 - 01 Jan 2020
Abstract
The modelling of metabolic activation of the benzofuran nucleus is important to obtain eco-sustainable degradation methods and to understand the related mechanisms. The present work reports the catalytic oxidation of benzofuran, 2-methylbenzofuran, and 3-methylbenzofuran by hydrogen peroxide, at room temperature, in the presence [...] Read more.
The modelling of metabolic activation of the benzofuran nucleus is important to obtain eco-sustainable degradation methods and to understand the related mechanisms. The present work reports the catalytic oxidation of benzofuran, 2-methylbenzofuran, and 3-methylbenzofuran by hydrogen peroxide, at room temperature, in the presence of different Mn(III) porphyrins as models of cytochrome P450 enzymes. Conversions above 95% were attained for all the substrates. The key step is the formation of epoxides, which undergo different reaction pathways depending on factors, such as the position of the methyl group and the reaction and work-up conditions used. Full article
(This article belongs to the Special Issue Recent Developments on Catalysis by Metalloporphyrins and Analogues)
Show Figures

Graphical abstract

Open AccessFeature PaperArticle
Second-Generation Manganese(III) Porphyrins Bearing 3,5-Dichloropyridyl Units: Innovative Homogeneous and Heterogeneous Catalysts for the Epoxidation of Alkenes
Catalysts 2019, 9(11), 967; https://doi.org/10.3390/catal9110967 - 16 Nov 2019
Cited by 1
Abstract
The synthesis, characterisation and homogeneous catalytic oxidation results of two manganese(III) porphyrins of the so-called second-generation of metalloporphyrin catalysts, containing one or four 3,5-dichloropyridyl substituents at the meso positions are reported for the first time. The catalytic efficiency of these novel manganese(III) porphyrins [...] Read more.
The synthesis, characterisation and homogeneous catalytic oxidation results of two manganese(III) porphyrins of the so-called second-generation of metalloporphyrin catalysts, containing one or four 3,5-dichloropyridyl substituents at the meso positions are reported for the first time. The catalytic efficiency of these novel manganese(III) porphyrins was evaluated in the oxidation of cyclooctene and styrene using aqueous hydrogen peroxide as the oxidant, under homogeneous conditions. High conversions were obtained in the presence of both catalysts, obtaining the corresponding epoxide as the major product. The asymmetric metalloporphyrin, chloro[5,10,15-tris(2,6-dichlorophenyl)-20-(3,5-dichloropyridin-4-yl)porphyrinate]manganese(III), CAT-4, evidences a similar activity to that obtained with the well-known and highly efficient second-generation metalloporphyrin catalyst, chloro[5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinate]manganese(III), CAT-2. CAT-4 was covalently attached onto Merrifield resin and 3-bromopropylsilica supports. The solid materials obtained were characterized by several techniques including diffuse reflectance, UV—VIS spectrophotometry, SEM and XPS. The catalytic results for the oxidation of cyclooctene and styrene using the immobilized catalysts are also presented. The Merrifield-supported catalyst showed to be very efficient, leading to five catalytic cycles in the oxidation of cyclooctene, using tert-butyl hydroperoxide as the oxidant. Full article
(This article belongs to the Special Issue Recent Developments on Catalysis by Metalloporphyrins and Analogues)
Show Figures

Graphical abstract

Open AccessArticle
Studies of the Catalytic Activity of Iron (III) Porphyrins for the Protection of Carbonyl Groups in Homogeneous Media
Catalysts 2019, 9(4), 334; https://doi.org/10.3390/catal9040334 - 04 Apr 2019
Cited by 1
Abstract
The protection of carbonyl groups that produce acetal products is a key reaction in fine chemistry due to the high reactivity of aldehydes and ketones in certain media. This process can be catalyzed by protic or Lewis acids. Since metalloporphyrins often possess free [...] Read more.
The protection of carbonyl groups that produce acetal products is a key reaction in fine chemistry due to the high reactivity of aldehydes and ketones in certain media. This process can be catalyzed by protic or Lewis acids. Since metalloporphyrins often possess free axial positions in the central metal, they can be applied as Lewis acid catalysts, allowing the additional coordination of substrates. Therefore, three ferric complexes were selected to be evaluated as catalysts for the acetalization of benzaldehyde with ethanol and triethyl orthoformate (TEOF) in the homogeneous phase: (i) 5,10,15,20-tetrakis(phenylporphyrin) iron (III) chloride (Fe0F); (ii) 5,10,15,20-tetrakis(2,6-difluorphenylporphyrin) iron (III) chloride (Fe2F); and (iii) 5,10,15,20-tetrakis(pentafluorphenylporphyrin) iron (III) chloride (Fe5F). The complex Fe5F showed the highest catalytic activity, and kinetic parameters were evaluated for this reaction, exhibiting an increasing rate of reaction of about 550-fold in comparison with the non-catalyzed reaction. The reaction scope was also investigated, and Fe5F was found to be active for the acetalization of benzaldehyde and acetophenone, with different protective agents such as alcohols, glycols, glycerol, and epoxide being selective for the formation of cyclic acetals. The protection of benzaldehyde with ethylene glycol and propylene glycol were also studied at different temperatures, and turnover frequency (TOF) values of up to 360 h−1 were determined at 40 °C in homogenous media without the need for solvent or drying agents. Full article
(This article belongs to the Special Issue Recent Developments on Catalysis by Metalloporphyrins and Analogues)
Show Figures

Graphical abstract

Open AccessArticle
Tin(IV)-Porphyrin Tetracarbonyl Cobaltate: An Efficient Catalyst for the Carbonylation of Epoxides
Catalysts 2019, 9(4), 311; https://doi.org/10.3390/catal9040311 - 29 Mar 2019
Cited by 2
Abstract
Cationic tin(IV) porphyrins with tetracarbonyl cobaltates were synthesized, exhibiting bifunctional catalytic reactivity. The Lewis acidic tin-porphyrin center activated epoxides; concurrently, cobalt carbonyl anions efficiently opened epoxides and delivered carbonyl moieties. Thus, a series of β-lactones with a high synthetic value were obtained. This [...] Read more.
Cationic tin(IV) porphyrins with tetracarbonyl cobaltates were synthesized, exhibiting bifunctional catalytic reactivity. The Lewis acidic tin-porphyrin center activated epoxides; concurrently, cobalt carbonyl anions efficiently opened epoxides and delivered carbonyl moieties. Thus, a series of β-lactones with a high synthetic value were obtained. This catalytic system showed excellent efficiency exceeding a turnover number of one thousand with a broad substrate scope. In addition, the presented tin porphyrin-based catalyst exhibited exclusive chemoselectivity to terminal epoxides over internal ones. The selective carbonylation of di-epoxides demonstrated the usefulness of these catalysts in the synthesis of complex molecular structures. Full article
(This article belongs to the Special Issue Recent Developments on Catalysis by Metalloporphyrins and Analogues)
Show Figures

Scheme 1

Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

Title: Cyclopropanation Reactions Catalyzed by Metalloporphyrins Bound to Gold Nanoparticles
Author: Pietro Tagliatesta
Affiliation: Dipartimento di Chimica, Università degli Studi di Roma “Tor Vergata”, Rome, Italy
Correspondence: [email protected]

Title: Direct and Multiple Functionalization of the Benzofuran Core by Mn(III)porphyrin Catalytic Oxidation
Authors: Craig John Medforth
Affiliations: Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre, 687, 4169-007 Porto, Portugal
Correspondence: [email protected]

Title: Acetalization of carbonyl compounds catalyzed by ironporphyrins
Authors: Gabriel Kaetan Baio Ferreira, Charles Carvalho, Shirley Nakagaki*
Affiliations: Laboratório de Bioinorgânica e Catálise, Departamento de Química - Centro Politécnico, Universidade Federal do Paraná (UFPR), Curitiba – PR, Brazil
Correspondence: [email protected]
Abstract: Protection of carbonyl groups giving acetal products is a key reaction in fine chemistry due to the high reactivity of aldehydes and ketones in certain media and this processes may be catalyzed by protic or Lewis acids. Since metalloporphyrins often possess free axial positions in the central metal, they can be applied as Lewis acid catalysts allowing additional coordination of substrates. In this way we selected three iron(III)porphyrins to be tested as catalysts towards acetalization of benzaldehyde with ethanol and triethyl orthoformate (TEOF) in homogeneous phase: [tetraphenylporphyrin iron(III)], [tetra(2,6-difluorphenyl)porphyrin iron(III)] and [tetra(2,3,4,5,6-pentafluorphenyl)porphyrin iron (III)]. The full fluorinated complex showed the highest catalytic activity and kinetic parameters were evaluated for this reaction, exhibiting an increasing in the rate of the reaction of 551-fold in comparison to the non-catalyzed reaction. The reaction scope was also investigated and the catalyst was active for the acetalization of benzaldehyde and acetophenone with different protective groups, such as alcohols, glycols, glycerol and epoxide, presenting selectivity for the protection of aldehyde with ethylene- and propyleneglycol giving cyclic acetals–up to 99% of conversion in 30 min at 40 ºC with no solvent.


 

Back to TopTop