Chemical Reactions Catalyzed by Metalloporphyrin-Based Metal-Organic Frameworks

Abstract

Abstract:The synthetic versatility and the potential application of metalloporphyrins (MP) in different fields have aroused researchers' interest in studying these complexes, in an attempt to mimic biological systems such as cytochrome P-450. Over the last 40 years, synthetic MPs have been mainly used as catalysts for homogeneous or heterogeneous chemical reactions. To employ them in heterogeneous catalysis, chemists have prepared new MP-based solids by immobilizing MP onto rigid inorganic supports, a strategy that affords hybrid inorganic-organic materials. More recently, materials obtained by supramolecular assembly processes and containing MPs as building blocks have been applied in a variety of areas, like gas storage, photonic devices, separation, molecular sensing, magnets, and heterogeneous catalysis, among others. These coordination polymers, known as metal-organic frameworks (MOFs), contain organic ligands or complexes connected by metal ions or clusters, which give rise to a 1-, 2-or 3-D network. These kinds of materials presents large surface areas, Brønsted or redox sites, and high porosity, all of which are desirable features in catalysts with potential use in heterogeneous phases. Building MOFs based on MP is a good way to obtain solid catalysts that offer the advantages of bioinspired systems and zeolitic materials. In this mini review, we will adopt a historical approach to present the most relevant MP-based MOFs applicable to catalytic reactions such as oxidation, reduction, insertion of functional groups, and exchange of organic functions. OPEN ACCESS

Porphyrins as Catalysts in Scalable Organic Reactions

“…The epoxidation of alkenes is one of the processes of great importance in the fine chemical industry from an economic point of view, because epoxides are useful intermediates in the production and manufacture of high-value commercial polymers like polyurethane, polyamides, resins, and polyesters [31]. In addition, this transformation is used to carry out bioinspired oxidations [32] to produce drug candidates or metabolites (Scheme 3).…”

Highly thermally stable heterogeneous catalysts: study of 0D and 3D porphyrinic MOFs

“…18 Accordingly, metalloporphyrinic materials can reproduce the natural functions of porphyrins and move them to molecular level structured systems and nanotechnological devices. 19,20 In this sense, porphyrin-based MOFs are reporting great results, [21][22][23] since Suslick et al reported the first catalytic activity of a porphyrinic coordination polymer with open structure. 24 In the last years, porphyrinic complexes of iron, 25 cobalt, 26 ruthenium, 27 rhodium, 28 among others, are known in literature to catalyze chemical reactions like, for example, olefin cyclopropanation and X-H (X = C, N, Si) bond insertion with high efficiency and selectivity.…”

Synthesis of new metalloporphyrin derivatives from [5,10,15,20-tetrakis (pentafluorophenyl)porphyrin] and 4-mercaptobenzoic acid for homogeneous and heterogeneous catalysis

“…As expected, the free-base porphyrin P2 afforded the corresponding complexes FeP2 and MnP2 (Figure 2), which were soluble in most organic solvents A c c e p t e d M a n u s c r i p t MOFs are solids that originate from binding between organic or inorganic molecules and metal clusters, which results in a robust and often nanoporous bi-or tridimensional supramolecular structure [12,54]. Supramolecular systems based on porphyrins can display various kinds of interactions: a ligand group can interconnect the macrocycles (van der Waals interactions), or one donor atom present in the metalloporphyrin can bind to the metal center of another metalloporphyrin [12].…”

“…This absence of signal was observed for the MnP2 EPR analysis but nevertheless, as described in the previous paragraph, an EPR signal emerged at g = 2.0 ( Figure S17) for the solid MnP6, which could refer to the existence of Mn(II) ions that probably acted as coordinative ions for the peripheral acid groups present in the ring of porphyrin P6. This coordination should generate and stabilize the structured solid MnP6 [12].…”