A Carrier-Free Recyclable Rh/Terpyridine Catalyst for Alkene Hydroformylation: Homogeneous Catalysis and Heterogeneous Separation

Industrial & Engineering Chemistry Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

Hydroformylation of alkenes is one the most important industrial processes for production value-added aldehydes. A new square-planar geometry rhodium(I) complex, RhI(CO)(terpyridine), has been synthesized and characterized using nuclear magnetic resonance (NMR), electrospray ionization mass spectrometry (ESI-MS), single-crystal X-ray diffraction (XRD), scanning electron microscopy (SEM). This complex crystallizes in a self-replicating manner through RhI···RhI π–π interactions at room temperature, allowing it to function as carrier-free recyclable rhodium catalyst hydroformylation various alkenes, which effectively addresses challenge associated with separation catalysts from products. The unique packing model enables RhI(CO)(terpyridine) partially dissolve under conditions, thereby acting homogeneous catalyst. Furthermore, maintains both consistent reactivity structural integrity cyclohexene reactions over 10 recycling runs standard reaction conditions (40 bar, 100 °C, 4 h). Additionally, integrated advantages catalysis heterogeneous separation, demonstrated by its high robust recyclability long-chain C6–C18 α-methylstyrene, mixed octenes, highlighting potential applications.

Language: Английский

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MOF‐Supported Heterogeneous Catalysts for Hydroformylation Reactions: A Minireview

ChemCatChem, Journal Year: 2023, Volume and Issue: 16(7)

Published: Dec. 20, 2023

Abstract Transition metal‐catalyzed hydroformylation reaction of olefins is one the most important transformations in perspective both industrial applications and academic research. This synthetic process provides a straightforward easy way for inexpensive feedstock (mostly different alkene molecules) to valuable aldehyde compounds, which are considered as major building blocks several essential chemical products. Inspired motivated by tremendous success homogeneous catalysis reactions, paramount interests have been raised design development active heterogeneous catalysts owning advantages from molecular material sciences. Crystalline metal‐organic frameworks (MOFs) solid support immobilize shown appealing promises catalysts. review sketches out decade developments MOF‐based while discussing limitations their implementation beyond lab scale.

Language: Английский

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Low‐Valent Metals in Metal‐Organic Frameworks Via Post‐Synthetic Modification

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Aug. 24, 2023

Metal-organic frameworks (MOFs) provide uniquely tunable, periodic platforms for site-isolation of reactive low-valent metal complexes relevance in modern catalysis, adsorptive applications, and fundamental structural studies. Strategies integrating such species MOFs include post-synthetic metalation, encapsulation direct synthesis using organometallic as building blocks. These approaches have each proven effective enhancing catalytic activity, modulating product distributions (i.e., by improving selectivity), providing valuable mechanistic insights. In this minireview, we explore these different strategies, applied to isolate within MOFs, with a particular focus on examples that leverage the unique crystallinity, permanent porosity chemical mutability achieve deep insights lead new paradigms field hybrid catalysis.

Language: Английский

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Concomitant role of metal clusters and ligands in the synthesis and control of porosity in Metal-Organic Frameworks: A literature review

Results in Chemistry, Journal Year: 2023, Volume and Issue: 6, P. 101206 - 101206

Published: Nov. 10, 2023

A clossal increase in the number of research articles on metal–organic frameworks (MOFs) have recently been anticipated as next-generation functional materials. The characteristic coordination behavior between metal ion and organic linker MOFs provide them hydrid features both moieties. For substantial improved performance to achieve widespread applications diverse fields, it is essential develop effective synthetic strategies understand role cluster or sphere secondary building units (SBU's) detail. augmentation porosity large surface area with multitude topologies a boost for application these materials allied fields. This review article provides detailed introduction porous MOF materials; encompassing linkers defining Detailed investigations about clusters expanded that lead ultrahigh done portrayed carefully. structural aspects zirconium, zinc copper based (porphyrin pyrene based) thoroughly owing their various will better understanding factors involved synthesis controll toward desired applications.

Language: Английский

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Metal−Organic Framework‐Induced Rh Monocoodination on Diphosphine Ligand Enables Catalytic Hydroformylation of Aliphatic Olefins at Room Temperature and Pressure

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 11, 2024

Abstract Persistent challenges in hydroformylation of olefins include controlling regioselectivity, particularly for short aliphatic and conducting reactions under ambient conditions. We report here the synthesis monophosphine–Rh complexes on a typical chelated diphosphine ligand mediated by Zr‐MOF through isolating pair phosphorus atoms. demonstrate that single‐crystal X‐ray diffraction can elucidate structural transformation Rh catalyst during olefin hydroformylation, providing valuable information active site reconstruction catalysis. The Rh‐MOF demonstrates excellent catalytic recyclable performance with linear to branched ratios up 99 : 1. Due framework‘s capacity adsorb concentrate gases, occur room temperature pressure, eliminating need high pressures typically required homogeneous systems. This study show Zr–MOF be unique platform synthesizing unusual species cannot exist solutions meaningful chemical transformations pertaining metal‐based

Language: Английский

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Dual-site catalyzed heterogeneous hydroformylation-aldol condensation tandem reaction in phosphinized microenvironment over MOF-808

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: 506, P. 160033 - 160033

Published: Jan. 1, 2025

Language: Английский

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Tuning the regioselectivity of heterogeneous hydroformylation by engineering carbon species microenvironment around Rh sites

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 116095 - 116095

Published: March 1, 2025

Language: Английский

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MOF-Supported Diphosphine Ligands for Iridium-Catalyzed C–H Borylation of Arenes

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Postsynthetic methods have been used to immobilize a carboxylate-functionalized diphosphine ligand, N,N-bis[(diphenylphosphino)methyl]glycinate (dppmg), in different metal-organic framework (MOF) supports. H(dppmg) reacts quantitatively with Zn-OH groups MFU-4l-OH (1) provide solid-state ligands (1-H-x) controllable loadings. metalation [Ir(OMe)(cod)]2 (cod = 1,5-cyclooctadiene) generates heterogeneous precatalysts (1-Ir-x) that show excellent activity toward C-H borylation of arenes. This is dependent on both the catalyst site density and initial concentration borylating reagent. Homogeneous catalysts supported by analogous exhibit low catalytic activity, demonstrating beneficial role isolation. Immobilization dppmg-Ir at Zr-based nodes MOF-808 (2-P-Ir) NU-1000 (3-P-Ir) results materials relatively poor toluene, revealing importance MOF support design.

Language: Английский

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Recent advance in metal-organic frameworks based catalysts for production of fine chemicals via thermal catalysis

Molecular Catalysis, Journal Year: 2025, Volume and Issue: 573, P. 114811 - 114811

Published: Jan. 7, 2025

Language: Английский

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Tuning the Regioselectivity of Heterogeneous Hydroformylation by Engineering Carbon Species Microenvironment Around Rh Sites

Published: Jan. 1, 2025

Olefin hydroformylation is one of the most important industrial processes for aldehyde synthesis. Heterogeneous catalysts are easy to separate compared with homogenous catalysts, yet limited success in activity and regioselectivity control. In present work, a zeolite-encapsulated rhodium carbide species (RhCx@S-1) catalyst was developed, demonstrating not only relatively high catalytic but also good stability heterogeneous propylene hydroformylation. The unique microenvironment formed situ during carbonization reduction process, tuning steric electronic characteristics Rh obtain more liner aldehydes. This work shows an alternative strategy promote olefin catalyzed by zeolite-confined provides insights into selective regulation catalysts.

Language: Английский

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