Electrocatalytic Formate Oxidation by Cobalt–Phosphine Complexes DOI

Sriram Katipamula,

Andrew W. Cook,

Isabella Niedzwiecki

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1771 - 1781

Published: Jan. 17, 2025

We report a family of cobalt complexes based on bidentate phosphine ligands with two, one, or zero pendent amine groups in the ligand backbone. The are active electrocatalysts for formate oxidation reaction, generating CO2 near-quantitative faradaic efficiency at moderate overpotentials (0.45–0.57 V acetonitrile). Thermodynamic measurements reveal that these energetically primed via hydride transfer to center, followed by deprotonation resulting cobalt-hydride acting as base. complex featuring single arm is fastest electrocatalyst this series, an observed rate constant 135 ± 8 h–1 25 °C, surpassing activity bis-pendent analogue. Electrocatalytic turnover not no groups: decomposition evident presence high concentrations. Thus, application thermodynamic considerations design demonstrated successful strategy, while also highlighting delicate balance properties necessary achieving productive turnover.

Language: Английский

Ligand-Bound CO2 as a Nonclassical Route toward Efficient Photocatalytic CO2 Reduction with a Ni N-Confused Porphyrin DOI

Huihong Yuan,

Akash Krishna,

Zhihe Wei

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10550 - 10558

Published: April 8, 2024

Implementing the synergistic effects between metal and ligand has successfully streamlined energetics for CO2 activation gained high catalytic activities, establishing important breakthroughs in photocatalytic reduction. Herein, we describe a Ni(II) N-confused porphyrin complex (NiNCP) featuring an acidic N–H group. It is readily deprotonated exists anion form during catalysis. Owing to this functional site, NiNCP gave rise outstanding turnover number (TON) as 217,000 with 98% selectivity reduction CO, while parent (NiTPP) was found be nearly inactive. Our mechanistic analysis revealed nonclassical reaction pattern where effectively activated via attack of Lewis-basic ligand. The resulting ligand-bound adduct could further reduced produce CO. This new metal–ligand effect anticipated inspire design highly active catalysts small molecule activations.

Language: Английский

Citations

22
Research on transition metals for the multicomponent synthesis of benzo-fused γ-lactams DOI Creative Commons
Fadhil Faez Sead, Vicky Jain,

Suhas Ballal

et al.

RSC Advances, Journal Year: 2025, Volume and Issue: 15(4), P. 2334 - 2346

Published: Jan. 1, 2025

Benzo-fused γ-lactams are fundamental in medicinal chemistry, acting as essential elements for various therapeutic agents due to their structural adaptability and capability enhance biological activity.

Language: Английский

Citations

6
Copper Catalyzed Formation of Carbon–Silicon Bond: A Review DOI
Rafid Jihad Albadr,

Waam Mohammed Taher,

Mariem Alwan

et al.

Journal of Inorganic and Organometallic Polymers and Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 1, 2025

Language: Английский

Citations

4
Control of Selectivity in Homogeneous Catalysis through Noncovalent Interactions DOI Creative Commons
Kamran T. Mahmudov⧫, Armando J. L. Pombeiro

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(26)

Published: Feb. 23, 2023

The regio-, site-, stereo- or chemoselective homogeneous catalytic transformations are extremely important for the growth/success of current chemical industry. Based on empirical, theoretical intuitive knowledge, several synthetic strategies, such as ligand design, transient directing group, metal node alternation, metal-ligand cooperation, pore decoration, biomimetic, have already been developed selective functionalization organic substrates. In comparison to other tactics, use noncovalent interactions control selectivity in compounds may avoid multi-steps, reduce time procedure, decrease cost operation, and increase reactivity catalyst. fact, enzymes achieve a high through biochemical processes Nature. Guided by impressive performance biosynthesis biodegradation reactions, various types complex organocatalysts developed, which catalyst-substrate pivotal impact distinctive stabilization transition states intermediates, improving efficiency reactions. Herein, we highlight recent relevant examples directing/driving function transformation substrate(s) catalyzed both catalysts.

Language: Английский

Citations

31
Light‐Responsive Supramolecular Liquid‐Crystalline Metallacycle for Orthogonal Multimode Photopatterning DOI Open Access

Yi‐Xiong Hu,

Xingtian Hao,

Dan Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(4)

Published: Nov. 15, 2023

Abstract The development of multimode photopatterning systems based on supramolecular coordination complexes (SCCs) is considerably attractive in chemistry and materials science, because SCCs can serve as promising platforms for the incorporation multiple functional building blocks. Herein, we report a light‐responsive liquid‐crystalline metallacycle that constructed by coordination‐driven self‐assembly. By exploiting its fascinating liquid crystal features, bright emission properties, facile photocyclization capability, unique system with spatially‐controlled fluorescence‐resonance energy transfer (FRET) built through introduction photochromic spiropyran derivative, which led to realization first example orthogonal three‐modes, namely holography, fluorescence, photochromism.

Language: Английский

Citations

30
Hydrogen-bond-acceptor ligands enable distal C(sp3)–H arylation of free alcohols DOI
Daniel A. Strassfeld, Chia-Yu Chen, Han Seul Park

et al.

Nature, Journal Year: 2023, Volume and Issue: 622(7981), P. 80 - 86

Published: Sept. 6, 2023

Language: Английский

Citations

29
Iron-Catalyzed Asymmetric Imidation of Sulfides via Sterically Biased Nitrene Transfer DOI
Zhenzhong Liu, Hongli Wu,

H Huiqi Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 18050 - 18060

Published: June 15, 2024

Transition-metal-catalyzed enantioselective nitrene transfer to sulfides has emerged as one of the most powerful strategies for rapid construction enantioenriched sulfimides. However, achieving stereocontrol over highly active earth-abundant transition-metal nitrenoid intermediates remains a formidable challenge compared with precious metals. Herein, we disclose chiral iron(II)/N,N′-dioxide-catalyzed imidation dialkyl and alkyl aryl using iminoiodinanes precursors. A series sulfimides were obtained in moderate-to-good yields high enantioselectivities (56 examples, up 99% yield, 98:2 e.r.). The utility this methodology was demonstrated by late-stage modification complex molecules synthesis insecticide sulfoxaflor related bioactive compounds. Based on experimental studies theoretical calculations, water-bonded high-spin iron species identified key intermediate. observed stereoselectivity original from steric repulsion between amide unit ligand cave bulky substituent sulfides. Additionally, dioxazolones proved be suitable acylnitrene precursors presence an iron(III)/N,N′-dioxide complex, resulting formation enantioselectivity-reversed (14 81% 97:3

Language: Английский

Citations

11
Rhodium‐Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation of 1,3‐Dipolar Nitrones DOI

Liren Xu,

Tilong Yang, Hao Sun

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Feb. 17, 2024

Abstract Owing to their distinctive 1,3‐dipolar structure, the catalytic asymmetric hydrogenation of nitrones hydroxylamines has been a formidable and longstanding challenge, characterized by intricate enantiocontrol susceptibility N−O bond cleavage. In this study, transfer were accomplished with tethered TsDPEN‐derived cyclopentadienyl rhodium(III) catalyst (TsDPEN: p ‐toluenesulfonyl‐1,2‐diphenylethylene‐1,2‐diamine), reaction proceeds via novel 7‐membered cyclic transition state, producing chiral up 99 % yield >99 ee. The practical viability methodology was underscored gram‐scale reactions subsequent transformations. Furthermore, mechanistic investigations DFT calculations also conducted elucidate origin enantioselectivity.

Language: Английский

Citations

9
High Performance Polyoxometalate-Stabilizing Pt Nanocatalysts for Quinoline Hydrogenation with Water-Mediated Dynamic Hydrogen DOI

Xinjia Wei,

Yongjun Jiang,

Yuan Ma

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 5344 - 5355

Published: March 26, 2024

In this work, a Keggin-type platinum substituted polyoxometalate (POM) is constructed by the reaction of monolacunary phosphotungstate precursor [PW11O39]7– with chloroplatinic acid. The as-obtained tetrabutylammonium salt (TBA-PWPt) demonstrates that dimeric Pt2+ ions are incorporated into POM frameworks and linked two anions. Notably, once Pt-substituted anion reduced H2, anion-stabilizing Pt nanocatalysts generated, which greatly facilitates forming oxygen vacancies adjacent to Pt0 species. show superior catalytic activity stability for selective hydrogenation quinoline 1,2,3,4-tetrahydroquinoline in water. Detailed investigations elucidate stronger adsorption on surface H2 activated at POMs-Pt interface site. Moreover, density functional theory (DFT) calculations H2O adsorbed interfacial then undergoes homolytic dissociation produce hydroxyl group (OH–) hydride (H–) H– species transferred N-containing pyridine ring hydrogenation, OH– help promote heterolytic H+ Sequentially, produced proton groups generate H2O, cycle completed.

Language: Английский

Citations

9
Recovery of chemicals and energy through thermo-chemical processing of plastic waste DOI
Taewoo Lee,

Dohee Kwon,

Sangyoon Lee

et al.

Progress in Energy and Combustion Science, Journal Year: 2025, Volume and Issue: 108, P. 101219 - 101219

Published: Jan. 16, 2025

Language: Английский

Citations

1