Ru Metalloligands Participate in the Construction of POM@MOF for Enhancing the Visible Photoinduced Baeyer–Villiger Oxidation Reaction DOI

Luoning Li,

Yanan Liu, Jing Wang

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(52), P. 24506 - 24516

Published: Dec. 17, 2024

Directed synthesis of high-efficiency visible photoinduced Baeyer–Villiger oxidation catalysts is primary significance. Here, the isopolymolybdate anion [β-Mo8O26]4– for first time encapsulated with photosensitive metalloligand [Ru(bpy)2(H2dcbpy)]2+ (bpy = 2,2′-bipyridine; H2dcbpy 2,2′-bipyridine-5,5′-dicarboxylic acid) to synthesize polyoxometalate@metal–organic frameworks, {(CdDMF)2[Ru(bpy)2(dcbpy)]3([β-Mo8O26])}·5DMF (Ru–Mo8). The composite photocatalyst Ru–Mo8 not only has a light absorption 700 nm but also shortens photogenerated electron transfer distances and accelerates charge proton transfer. can perform high selectivity up 96.7% yield under (λ > 400 nm) irradiation. turnover number frequency reaction were computed be 967 548 h–1, respectively, apparent quantum was 6.84% by 425 nm. Simultaneously, radical mechanism in O2/benzaldehyde system irradiation proposed.

Language: Английский

Fabrication of high-performing PW11Mn@MIL-101 nanocomposites for eco-efficient synthesis of cyclic carbonate DOI

M. S. E. Shafie,

Ali Khatib Juma,

Abdurrashid Haruna

et al.

Inorganic Chemistry Communications, Journal Year: 2025, Volume and Issue: unknown, P. 114003 - 114003

Published: Jan. 1, 2025

Language: Английский

Citations

1
NHPI catalyzed air oxidation of cyclohexanone: Mechanism and kinetics study DOI Open Access
Guanwen Chen, Bo Yuan, Ruolin Wang

et al.

The Canadian Journal of Chemical Engineering, Journal Year: 2025, Volume and Issue: unknown

Published: March 17, 2025

Abstract As an important monomer material for synthesizing polycaprolactone, ε‐caprolactone (ε‐CL), is currently produced through the Baeyer–Villiger oxidation of cyclohexanone. a green and promising process to produce ε‐CL, oxidizing cyclohexanone with air in presence sacrificial agents has attracted extensive attention from academia industry. However, slow reaction kinetic weak capacity limits application this technology. Herein, we used N‐hydroxyphthalimide (NHPI) as higdhly efficient homogeneous catalyst Through investigating influence conditions such temperature, gas velocity, aldehyde‐ketone ratio, solvent ratio on conversion rate selectivity optimum condition was obtained production high 3.43 mmol/gcat/min 90%. The mechanism investigated in‐situ UV–visible spectra, electron paramagnetic resonance (EPR) starch/KI experiment, plausible mechanistic mode involving three pivotal reactions proposed. dynamic model constructed validate proposed provide good predictions actual rate. This work provides meaningful insights into NHPI‐catalyzed cyclohexanone, theoretical guidance scale‐up processes.

Language: Английский

Citations

0
Visible-Light-Responsive Tetranuclear Ir-Based Polyoxometalates Achieve Photocatalytic Baeyer–Villiger Oxidation of Ketones DOI

Zelong Yuan,

Jing Wang, Huafeng Li

et al.

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

Published: March 18, 2025

Synthesizing efficient photocatalysts with a broad-spectrum response is crucial for improving solar energy utilization. In this work, we have constructed two examples of tetrameric Ir-based polyoxometalates by introducing an Ir ion. The introduction ions lowers the band gap energy, and light absorption range extended into visible region. Both displayed satisfactory reactivity visible-light-catalyzed Baeyer-Villiger reaction cyclohexanone, especially compound 1, which reacted up to 95.1% yield 3 h TON TOF values 951 510 h-1, respectively. Meanwhile, 1 also presents excellent cyclic structural stability, can still reach 92.2% after five reactions.

Language: Английский

Citations

0
Enhanced Oxidative Coupling of Thiols to Disulfides Using the Visible-Light-Responsive POM@MOF Constructed with Ru Metalloligands DOI

Luoning Li,

Yanan Liu, Jing Wang

et al.

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

Published: March 27, 2025

The photocatalytic oxidative coupling of thiols to disulfides by using visible light represents an economically viable and environmentally sustainable strategy. A novel POM@MOF photocatalyst (Ru–CdS–SiW) was synthesized through the encapsulation Keggin-type [SiW12O40]4– within a MOF composed Ru metalloligands {Cd4S2O16} clusters. In this structure, incorporation POMs MOFs reduced charge transport distance, facilitated separation transfer photogenerated charges holes, prevented recombination electron–hole pairs. Ru–CdS–SiW catalyst demonstrated exceptional catalytic performance, achieving 98.1% yield in S–S bond formation from 4-methylthiophenol with apparent quantum 4.8% at 440 nm. Through comprehensive exploratory experiments electron paramagnetic resonance (EPR) measurements, we elucidated mechanism underlying photoinduced thiols. Notably, reaction operates under mild visible-light conditions exhibits remarkable recyclability, presenting significant potential for applications sensitive systems, such as protein disulfide formation.

Language: Английский

Citations

0
[Ru(bpy)3]2+ Derivatives-Incorporated POM@MOFs with Good Photocatalytic Activity for Visible-Light-Driven Oxidative Coupling of Amines to Imines DOI
Zhen Jing,

Sen Liu,

Xiaodong Zhang

et al.

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

Published: April 8, 2025

Two novel POM@MOFs, {H3Zn2.5(H2O)10[Ru(dcbpy)3][PMo11VIMoVO40]}·2H2O (RuZn-PMo) and {H3Ni2.5(H2O)12[Ru(dcbpy)3][PMo11VIMoVO40]}·5H2O (RuNi-PMo), have been synthesized through a traditional hydrothermal method. They are composed of [Ru(bpy)3]2+-derived hexa-carboxylate Keggin-type anion [PMo11VIMoVO40]4-. In addition, their structures were well characterized by various spectroscopic methods. Under the irradiation visible light (λ > 400 nm), RuZn-PMo RuNi-PMo as heterogeneous photocatalysts showed efficient photocatalytic performance in coupling reaction amines, with TONs 451 454, respectively. Moreover, exhibited excellent reusability stability after three continuous cycles. Besides, EPR measurements performed to elucidate mechanism.

Language: Английский

Citations

0
In Situ Synthesis of Iron-Based Porphyrin Metal–Organic Frameworks for the Baeyer–Villiger Oxidation Using Air as an Oxidant DOI
Gang Liu, Yajun Zhao,

Chunying Chen

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 4, 2024

Iron-based porphyrin metal-organic frameworks (PMOFs) are a new type of material with good stability, catalytic activities, and reusability, which have broad application prospects. However, the synthesis iron-based PMOFs different metalloporphyrin units requires considerable amount reagents time. Herein, an in situ method was developed to simplify synthetic process PMOFs. A series highly stable (M

Language: Английский

Citations

1
Ru Metalloligands Participate in the Construction of POM@MOF for Enhancing the Visible Photoinduced Baeyer–Villiger Oxidation Reaction DOI

Luoning Li,

Yanan Liu, Jing Wang

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(52), P. 24506 - 24516

Published: Dec. 17, 2024

Directed synthesis of high-efficiency visible photoinduced Baeyer–Villiger oxidation catalysts is primary significance. Here, the isopolymolybdate anion [β-Mo8O26]4– for first time encapsulated with photosensitive metalloligand [Ru(bpy)2(H2dcbpy)]2+ (bpy = 2,2′-bipyridine; H2dcbpy 2,2′-bipyridine-5,5′-dicarboxylic acid) to synthesize polyoxometalate@metal–organic frameworks, {(CdDMF)2[Ru(bpy)2(dcbpy)]3([β-Mo8O26])}·5DMF (Ru–Mo8). The composite photocatalyst Ru–Mo8 not only has a light absorption 700 nm but also shortens photogenerated electron transfer distances and accelerates charge proton transfer. can perform high selectivity up 96.7% yield under (λ > 400 nm) irradiation. turnover number frequency reaction were computed be 967 548 h–1, respectively, apparent quantum was 6.84% by 425 nm. Simultaneously, radical mechanism in O2/benzaldehyde system irradiation proposed.

Language: Английский

Citations

1