Post-functionalized iridium Zr-MOF as a promising recycle catalyst for the hydrogenation of aromatics

[EN] The multifunctional heterogeneous catalyst iridium–Zr-based MOF is able to effectively catalyze the hydrogenation of aromatic compounds in high yields under mild conditions. The catalyst was found to be highly active and reusable, giving similar reactivity and selectivity after at least five catalytic uses.We thank the MINECO of Spain (project MAT2011-29020-C02-02), Consolider-Ingenio 2010-(CSD-0050-MULTICAT). for financial support. A.M.R.A. thanks MINECO for the FPI program.Rasero Almansa, AM.; Corma Canós, A.; Iglesias, M.; Sánchez Alonso, F. (2014). Post-functionalized iridium Zr-MOF as a promising recycle catalyst for the hydrogenation of aromatics. Green Chemistry. 16(7):3522-3527. https://doi.org/10.1039/c4gc00581cS3522352716

Synthesis of bimetallic Zr(Ti)-naphthalendicarboxylate MOFs and their properties as Lewis acid catalysis

Bimetallic Zr(Ti)-NDC based metal-organic frameworks (MOFs) have been prepared by incorporation of titanium(iv) into zirconium(iv)-NDC-MOFs (UiO family). The resulting materials maintain thermal (up to 500 °C), chemical and structural stability with respect to parent Zr-MOFs as can be deduced from XRD, N adsorption, FTIR and thermal analysis. The materials have been studied in Lewis acid catalyzed reactions, such as, domino Meerwein-Ponndorf-Verley (MPV) reduction-etherification of p-methoxybenzaldehyde with butanol, isomerization of α-pinene oxide and cyclization of citronellal.This work was supported by MINECO through the MAT2014-52085-C2-2 P project. A. M. R. A. is grateful to the MINECO for FPI fellowship

Multifunctional Iridium-Zr-MOF for N-alkylation of amines with alcohols and hydrogenation of arenes

Poster presented at the XXXII Conference GEQO, which is organised by the expert group meeting on organometallic chemistry, held in Tarragona (Spain) on September 17-19th, 2014.[Work hypothesis and objective] Zr-based MOF(UiO66-NH2) has a large specific surface area and pore size as well as good chemical resistance to water and organic solvents, which result in desirable properties for catalytic applications. This highly stable material was selected as support. We have developed a simple and efficient method for new readily recoverable hybrid catalyst that combines the catalytic activity of transition-metal complexes with the architecture of metal organic frameworks (MOFs) and their application for cascade reactions [1], N-akylation of alcohols [2] and hydrogenation of arenes [3].[Results] In the tested reactions, UiO-66-LIr can be recovered by simple filtration in air and reused without significant loss of catalytic activity, at least after 5 cycles while framework structures are maintained.The authors thank the MINECO of Spain (Projects MAT2011-29020-C02-02 and Consolider Ingenio 2010-MULTICAT.Peer Reviewe

Postsynthetic metal exchange of Ti(IV) into a series of mixed ligand UiO-MOFs: study of their catalytic applications

Poster presented at the 1st European Conference on Metal Organic Frameworks and Porous Polymers, held on October 11-14th, 2015, Potsdam (Germany).Herein, we report mixed-ligand, mixed-metal highly porous UiO-derivatives (UiO = University of Oslo) obtained by postsynthetic metal exchange (PSE)1. Ti atoms were embedded into the Zr-cluster of UiOs (Zr6O4(OH)4) by treatment with TiCl4(THF)2, obtaining up to 50% atom exchanged. After PSE, the crystallinity and morphology of the UiO-materials were maintained, indicating that Zr-Ti exchange did not alter the structural properties of the MOFs. Post-functionalized MOFs have demonstrated attractive properties for catalytic applications2. Herein Zr- and ZrTi-UiO-MOFs have been applied as catalysts for the isomerization of -pinene epoxide and citronellal. High conversions and good selectivities were obtained for both substrates (70 and 80% respectively in 24 hours). The presence of Ti into the catalyst improves the reactivity obtaining higher conversions, particularly in the case of citronellal, while the presence of NH2 group has minor effect on the reactions.Consolider Ingenio (CSD2009-0050, MULTICAT), MAT2011-29020-C02-02

Porous aromatic frameworks (PAFs) as efficient supports for N-heterocyclic carbene catalysts

Porous polymeric aromatic frameworks (PAFs) have high porosity and surface area, as well as high physicochemical stability; such characteristics are important in the design of heterogeneous catalysts with high catalytic efficiency and recyclability. This paper presents the synthesis, characterization, post-functionalization and catalytic performance of the resulting modified PAFs based on tetraphenyladamantane (PAF), tetraphenylmethane (PAF) and 9,9′-spirobisfluorene (PAF) nodes. The PAFs were obtained by the Suzuki-Miyaura cross-coupling under microwave heating, and were sequentially reacted with 1-(chloromethoxy)octane and 1-mesityl-1H-imidazole or 2-(1H-imidazol-1-yl)pyridine to yield the corresponding imidazolium chloride derivative (PAF-Im) which readily formed stable N-heterocyclic carbene (NHC) iridium and ruthenium complexes (PAF-(NHC)Ir, PAF-(NHC)Ru). The materials were characterized by solid-state NMR spectroscopy, FTIR spectroscopy, and textural analysis. The PAF-(NHC)M materials display excellent catalytic performance in the N-alkylation of amines with alcohols and transfer hydrogenation of ketones over multiple catalytic cycles.This work was supported by MINECO through the Consolider Ingenio 2009 (CSD-0050, MULTICAT), MAT2014-52085-C2-2-P projects. A. M. R. A. thanks MINECO for financial support

Bifunctional iridium-(2-aminoterephthalate)-Zr-MOF chemoselective catalyst for the synthesis of secondary amines one-pot three-step cascade reaction

[EN] A simple and efficient method for the synthesis of N-alkyl amines via a cascade reaction (hydrogenation + reductive amination) using a new recyclable hybrid catalyst that combines the catalytic power of transition metal complexes with the architecture of metal organic frameworks (MOFs). (C) 2012 Elsevier Inc. All rights reserved.We thank CONSOLIDER-INGENIO 2010-(CSD-0050-MULTICAT) and the MINECO of Spain (Project MAT2011-29020-C02-02) for financial supportPintado Sierra, M.; Rasero Almansa, AM.; Corma Canós, A.; Iglesias, M.; Sánchez, F. (2013). Bifunctional iridium-(2-aminoterephthalate)-Zr-MOF chemoselective catalyst for the synthesis of secondary amines one-pot three-step cascade reaction. Journal of Catalysis. 299:137-145. https://doi.org/10.1016/j.jcat.2012.12.004S13714529