A Cooperative Cobalt-Driven System for One-Carbon Extension in the Synthesis of (Z)-Silyl Enol Ethers from Aldehydes: Unlocking Regio- and Stereoselectivity DOI Creative Commons
Soumyashree Jena,

Lars Frenzen,

Vishal Chugh

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(51), P. 27922 - 27932

Published: Dec. 12, 2023

The research presented herein explores a cobalt-based catalytic system, distinctively featuring cooperative boron-centric element within its intricate ligand architecture. This system is strategically engineered to enable the integration of singular carbon atom into aldehydes, process culminating in production (Z)-silyl enol ethers. Beyond offering an efficient one-pot synthesis route, this method adeptly overcomes challenges inherent conventional techniques, such as need for large amounts additives, restrictive functional group tolerance, and extreme reaction temperatures. Initial mechanistic studies suggest potential role cobalt–carbene complex catalytically significant species underscore importance borane segment. Collectively, these observations highlight advancing bond activation pursuits.

Language: Английский

Cobalt-Cluster-Based Metal–Organic-Framework-Catalyzed Carboxylative Cyclization of Propargylic Amines with CO2 from Flue Gas DOI

Meng-Hua Tang,

Yan Wang, Zhi Fang

et al.

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

Published: Jan. 27, 2025

The fixation of carbon dioxide (CO2) directly from flue gas into valuable chemicals like 2-oxazolidinones is great significance for economic and environmental benefits, which typically catalyzed by noble-metal catalysts under harsh conditions. Herein, a novel 2-fold interpenetrated framework {[Co3(μ2-O)(TCA)2(HDPTA)2]·2H2O·2DMF}n [Co(II)-based metal-organic (Co-MOF)] containing [Co3] clusters highly dense amino groups (-NH2) dispersed in the channel was prepared, exhibiting high solvent/pH stability CO2 adsorption capacity (24.9 cm3·g-1). Catalytic experiments demonstrated that Co-MOF could catalyze carboxylative cyclization propargylic amines to generate with yields up 98% mild conditions gas. In addition, retained its structure catalytic activity after five-cycle experiments, showing promising practical application. Density functional theory (DFT) calculation suggested centers MOF activated C≡C much more binding energy than Co(NO3)2, partly accounting Co-MOF. This work demonstrates first Co-based material efficient as source, inspiring further rational design porous utilization.

Language: Английский

Citations

0
Unlocking the Metalation Applications of TMP‐powered Fe and Co(II) bis(amides): Synthesis, Structure and Mechanistic Insights DOI Creative Commons
Alessandra Logallo, Lewis C. H. Maddock, Manting Mu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: April 2, 2024

Abstract Typified by LiTMP and TMPMgCl.LiCl, (TMP=2,2,6,6‐tetramethylpiperidide), s‐block metal amides have found widespread applications in arene deprotonative metalation. On the contrary, transition lack sufficient basicity to activate these substrates. Breaking new ground this field, here we present synthesis full characterisation of earth‐abundant metals M(TMP) 2 (M=Fe, Co). Uncovering a reactivity profile towards fluoroarenes, amide complexes can promote direct M−H exchange processes regioselectively using one or two their basic arms. Remarkably, even when perfluorinated substrate, selective C‐H metalation occurs leaving C−F bonds intact. Their kinetic be boosted LiCl NBu 4 Cl additives which enables formation kinetically activated ate species. Combining spectroscopic structural studies with DFT calculations, mechanistic insights been gained on how low polarity take place. also used access ferrocene cobaltocene deprotonation cyclopentadiene undergo efficient CO insertion both groups under mild reaction conditions.

Language: Английский

Citations

3
Four-electron reduction of CO2: from formaldehyde and acetal synthesis to complex transformations DOI Creative Commons
Sarah Desmons, Julien Bonin, Marc Robert

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(37), P. 15023 - 15086

Published: Jan. 1, 2024

The expansive and dynamic field of the CO2 Reduction Reaction (CO2RR) seeks to harness as a sustainable carbon source or energy carrier. While significant progress has been made in two, six, eight-electron reductions CO2, four-electron reduction remains understudied. This review fills this gap, comprehensively exploring into formaldehyde (HCHO) acetal-type compounds (EOCH2OE, with E = [Si], [B], [Zr], [U], [Y], [Nb], [Ta] -R) using various CO2RR systems. These encompass (photo)electro-, bio-, thermal processes diverse reductants. Formaldehyde, versatile C1 product, is challenging synthesize isolate from CO2RR. also discusses acetal compounds, emphasizing their significance pathways distinct reactivity. Providing an overview state reduction, highlights achievements, challenges, potential produced - acetals sources for valuable product synthesis, including chiral compounds.

Language: Английский

Citations

3
Combined Computational and Experimental Investigation on the Mechanism of CO2 Hydrogenation to Methanol with Mn-PNP-Pincer Catalysts DOI Creative Commons

David A. Kuß,

Markus Hölscher, Walter Leitner

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(24), P. 15310 - 15322

Published: Nov. 30, 2022

A theoretical and experimental mechanistic study is presented for the homogeneously catalyzed CO2 hydrogenation to methanol, using an Mn-PNP-Pincer catalyst in presence of a Lewis acid cocatalyst alcohol as solvent. Quantum chemical computations at density functional theory DLPNO-CCSD(T) level suggest formate resting state most stable intermediate. The concerted activation dihydrogen via proton shuttle mechanism decomposition hemiacetal intermediate computed define turnover-determining transition state. resulting energy span calculated 34.5 kcal mol–1 theory. An Eyring plot reveals barrier reaction 31.4 under catalytic turnover conditions, showing good agreement with slight overestimation computational model. Concentration–time profiles involved species also locate experimentally rate-determining states (RDSs) ester methanol. measured kinetic isotope effects use H2/D2 EtOH/D are hydrogen splitting RDS, giving further support mechanism. These insights provide guidance reference future improvement catalysts based on abundant 3d metals CO2-based production

Language: Английский

Citations

14
Mechanism Insights into the Iridium(III)- and B(C6F5)3-Catalyzed Reduction of CO2 to the Formaldehyde Level with Tertiary Silanes DOI Creative Commons
Jefferson Guzmán, Asier Urriolabeitia, Marina Padilla

et al.

Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 61(50), P. 20216 - 20221

Published: Dec. 6, 2022

The catalytic system [Ir(CF3CO2)(κ2-NSiMe)2] [1; NSiMe = (4-methylpyridin-2-yloxy)dimethylsilyl]/B(C6F5)3 promotes the selective reduction of CO2 with tertiary silanes to corresponding bis(silyl)acetal. Stoichiometric and studies evidenced that species [Ir(CF3COO-B(C6F5)3)(κ2-NSiMe)2] (3), [Ir(κ2-NSiMe)2][HB(C6F5)3] (4), [Ir(HCOO-B(C6F5)3)(κ2-NSiMe)2] (5) are intermediates process. structure 3 has been determined by X-ray diffraction methods. Theoretical calculations show rate-limiting step for 1/B(C6F5)3-catalyzed hydrosilylation bis(silyl)acetal is a boron-promoted Si-H bond cleavage via an iridium silylacetal borane adduct.

Language: Английский

Citations

12
Cobalt‐Driven Cross‐Dehydrocoupling of Silanes and Amines for Silylamine Synthesis DOI
Ewelina Szafoni, Krzysztof Kuciński, Grzegorz Hreczycho

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(15)

Published: May 8, 2024

Abstract Cobalt complexes featuring triazine‐based PNP ligands have proven to be exceptionally active and chemoselective pre‐catalysts in facilitating the dehydrogenative coupling between silanes amines, leading synthesis of diverse aminosilanes. Notably, even challenging substrates exhibited high reactivity. The catalyst‘s unique feature avoiding with tertiary enhances process chemoselectivity. It facilitates a more precise silylamines possessing SiH 2 −N SiH−N motifs, overcoming challenges associated broader reactivity seen previous systems. In terms its remarkable chemoselectivity, it is also noteworthy that catalytic system exhibits both versatility efficacy converting untouched double triple carbon‐carbon bonds. This accomplishment particularly significant, given brought about by activity commonly employed catalysts competitive hydrosilylation process.

Language: Английский

Citations

2
Controlling hydrogen transfer dynamics in adaptive semihydrogenation of alkynes: Unveiling and directing outer- vs. inner-sphere mechanisms DOI Creative Commons
Vishal Chugh, Jiajun Wu, Markus Leutzsch

et al.

Chem Catalysis, Journal Year: 2024, Volume and Issue: 4(9), P. 101078 - 101078

Published: Aug. 20, 2024

Language: Английский

Citations

2
Concatenating Microbial, Enzymatic, and Organometallic Catalysis for Integrated Conversion of Renewable Carbon Sources DOI Creative Commons
Nina Klos, Ole Osterthun, Hendrik G. Mengers

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(12), P. 4546 - 4570

Published: Oct. 21, 2024

The chemical industry can now seize the opportunity to improve sustainability of its processes by replacing fossil carbon sources with renewable alternatives such as CO

Language: Английский

Citations

2
Catalytic materials based on metals (ions) used in the upcycling of plastics and polymers into fuels and valuable chemicals as part of sustainable development DOI
Kacper Pobłocki, Marta Pawlak, Joanna Drzeżdżon

et al.

Materials Science and Engineering R Reports, Journal Year: 2024, Volume and Issue: 162, P. 100881 - 100881

Published: Nov. 23, 2024

Language: Английский

Citations

2
One-Pot Synthesis of Dihydropyrans via CO2 Reduction and Domino Knoevenagel/oxa-Diels–Alder Reactions DOI
Kazuto Takaishi,

Ritsuki Nishimura,

Yuha Toda

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(9), P. 1370 - 1374

Published: Feb. 24, 2023

Catalytic CO2 reduction with phenylsilane under solvent-free conditions was linked the one-pot synthesis of 3,4-dihydropyrans from β-dicarbonyl compounds and styrenes. The includes three processes: (1) bis(silyl)acetal formation a domino reaction (2) Knoevenagel condensation (3) inverse-electron-demand oxa-Diels-Alder reaction. first process catalyzed by pentanuclear ZnII complex (0.07 mol %) to generate bis(silyl)acetals, which were hydrolyzed into formaldehyde be used in second step.

Language: Английский

Citations

6