The renaissance of oxo synthesis: heterogeneous Rh-catalyzed hydroformylation

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Language: Английский

---

Engineering atomic rhodium sites on conjugated porous monophosphine polymers for superior heterogeneously catalytic hydroformylation and hydrosilylation of alkenes

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 115977 - 115977

Published: Jan. 1, 2025

Language: Английский

---

Incorporation of low-valent metal ions in metal-organic frameworks and coordination polymers

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 531, P. 216491 - 216491

Published: Feb. 16, 2025

Language: Английский

---

Solid-State Phosphine Ligand Engineering via Postsynthetic Modification of Amine-Functionalized Metal–Organic Frameworks

Organometallics, Journal Year: 2024, Volume and Issue: 43(20), P. 2434 - 2442

Published: Jan. 31, 2024

Postsynthetic phospha-Mannich condensation has been investigated for the design of solid-state phosphine ligands using amine-functionalized metal–organic frameworks (MOFs). Hydroxymethylphosphine precursors Ph2P(CH2OH), PhP(CH2OH)2, and CyP(CH2OH)2 readily condense at 2-aminoterephthalate linkers MIL-101(Al)-NH2 IRMOF-3 to generate phosphine-functionalized MOFs MIL/IRMOF-PPh2-x, MIL/IRMOF-PPh-x, MIL/IRMOF-PCy-x, respectively, where x denotes loading per amine site. Solution-state 1H 31P{1H} nuclear magnetic resonance spectra base-digested reveal that PhP(CH2OH)2 react groups adjacent linkers, resulting in intraframework cross-linking. The phosphinated have as Ir-catalyzed C–H borylation arenes. MIL-PPh-0.1 MIL-PCy-0.1 exhibit good activity benchmark toluene when metalated with [Ir(OMe)(cod)]2 (cod = 1,5-cyclooctadiene). MIL-PPh2-0.1 derivatives show little or no catalytic turnover under same conditions, revealing connectivity MOF topology pore size are critical factors ligand design.

Language: Английский

---

Molecular Understanding of Heterogeneous Hydroformylation on Rh₁/CeO₂: Morphology Effects

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(21), P. 15956 - 15964

Published: Oct. 12, 2024

Heterogeneous hydroformylation enhances the separation process, avoiding use of phosphine ligands and reducing loss precious metals. However, enhancing catalytic activity elucidating reaction mechanisms remain challenging. In this work, we develop single-atom catalysts (SACs) Rh1/CeO2 with different morphologies study their structure–performance relationships at molecular level. The turnover frequency (TOF) Rh1/CeO2-Rod reaches 9386 h–1 a relatively high Rh loading (1.08 wt %), outperforming most reported SACs. presence oxygen atoms dangling bonds local stress surrounding embedded are identified as key factors behind morphology effects. Our work deepens understanding effects underlying enhancement paves way for future design highly active heterogeneous SACs both TOF optimal loading.

Language: Английский

---

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

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(49)

Published: Aug. 24, 2023

Abstract 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

---

Concepts of Ethylene Carbonylation with Hydrogen Gas and In‐Situ Generated Hydrogen

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(13)

Published: April 3, 2024

Abstract The carbonylation reaction of olefins is one the significant pathways for synthesis oxygen‐containing compounds such as aldehydes, esters, and amides. ethylene reactions have drawn much interest since they produce important chemicals propionaldehyde methyl propionate, which are crucial intermediates polymers. Moreover, carbonylation, coupled with C−C bond formation, shows great promise 3‐pentanone. However, due to presence various competing reactions, balancing activity selectivity has remained a challenge. This concept article aims at describing recent advances in different hydrogen sources.

Language: Английский

---

Novel Rh catalytic systems based on microporous metal-organic framework MIL-53(Al) for “green” ethylene hydroformylation

Journal of Porous Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 23, 2024

Language: Английский

---

From poison to promoter: investigation of supported rhodium sulphides as heterogeneous hydroformylation catalysts

Published: March 14, 2024

Herein we report the use of supported nanoparticles crystalline rhodium sulphides as active heterogeneous catalysts for hydroformylation alkenes showing an excellent selectivity towards aldehyde products. It was found that RhxSy (x=17, y=15 or x=2, y=3 with 1 and 10 wt.% Rh) greatly outperform pure Rh in terms activity, Rh17S15/SiO2 being superior catalyst candidate. The TOF styrene, determined lead system (1 Rh), is 2620 h-1 significantly higher than values reported phosphide-based systems. As presence S introduces structural diversity bulk well range potential catalytic surfaces, enumerate all possible terminations, local environment descriptors combined unsupervised Machine learning techniques DFT to draw structure performance relationships. We find on surface close proximity site had a profound impact chemical behavior catalyst, thus unlocking tunability properties. This allows affinity substrate be modulated high degree ranging from rich Rh-top like sites low; rich, particular Rh17S15, (Rh4) adsorption energies rivaling those pristine improved spatial resolution.

Language: Английский

---

From poison to promotor –unique Rh4 structural motifs in supported rhodium sulphides as hydroformylation catalysts

Published: May 3, 2024

The hydroformylation of alkenes is a cornerstone transformation for the chemical industry, central both functionalizing and extending carbon backbone an alkene. In our study, we explored silica-supported crystalline rhodium sulfide nanoparticles as heterogeneous catalysts in reactions, found that RhxSy systems (x=17, y=15 or x=2, y=3 with 1 wt.% Rh on SiO2) greatly outperform metallic nanoparticles. These proved to be exceptionally competitive when benchmarked against other cutting-edge terms activity, Rh17S15/SiO2 being superior catalyst candidate. By employing local environment descriptors, unsupervised machine learning density functional theory, have examined structure-performance relationships. Our results highlight presence S close proximity catalytic site unlocks tunability surface properties. This allows substrate affinity modulated, particular Rh17S15, adsorption energies rivaling those pristine improved spatial resolution.

Language: Английский

---