Challenges and recent advancements in the transformation of CO₂into carboxylic acids: straightforward assembly with homogeneous 3d metals

Chemical Society Reviews, Год журнала: 2022, Номер 51(22), С. 9371 - 9423

Опубликована: Янв. 1, 2022

The transformation of carbon dioxide (CO2) into useful chemicals, advanced materials, and energy is a long-standing challenge in both fundamental science industry. In recent years, utilization CO2 the presence inexpensive non-negligible environmentally friendly 3d metal-based catalysts (Fe, Mn, Co, Ni, Cu Ti) has become one most attractive topics. Particular attention been given to synthesis carboxylic acids their derivatives since these molecules serve as key intermediates chemical, fertilizer, pharmaceutical sectors. Considering numerous challenges linked with reactivity, number research groups have recently focused on by following thermo-, photo-, electrochemical strategies. However, facile access such remains vital catalysis organic owing high stability molecule which atom highest oxidation state. Another hurdle solve selectivity issue caused reaction different catalytic systems reactive functional group-containing molecules. Despite all issues, wide range transition applied this direction, but cheaper price inherent metals are at forefront domain. these, we aim summarise advances (over past five years) 3d-metal complexes reactivity towards activation for acids. Furthermore, discuss current trends, knowledge gaps, invigorating perspectives future advances.

Язык: Английский

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Challenges and Prospects in the Catalytic Conversion of Carbon Dioxide to Formaldehyde

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(46)

Опубликована: Сен. 6, 2022

Formaldehyde (HCHO) is a crucial C

Язык: Английский

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Unraveling the role of basic sites in the hydrogenation of CO2 to formic acid over Ni-based catalysts

Journal of Catalysis, Год журнала: 2024, Номер 430, С. 115357 - 115357

Опубликована: Фев. 1, 2024

Язык: Английский

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Chemical and Redox Noninnocence of Pentane-2,4-dione Bis(S-methylisothiosemicarbazone) in Cobalt Complexes and Their Application in Wacker-Type Oxidation

JACS Au, Год журнала: 2024, Номер 4(3), С. 1166 - 1183

Опубликована: Март 12, 2024

Cobalt complexes with multiproton- and multielectron-responsive ligands are of interest for challenging catalytic transformations. The chemical redox noninnocence pentane-2,4-dione bis(S-methylisothiosemicarbazone) (PBIT) in a series cobalt has been studied by range methods, including spectroscopy [UV–vis, NMR, electron paramagnetic resonance (EPR), X-ray absorption (XAS)], cyclic voltammetry, diffraction, density functional theory (DFT) calculations. Two [CoIII(H2LSMe)I]I [CoIII(LSMe)I2] were found to act as precatalysts Wacker-type oxidation olefins using phenylsilane, the role which was elucidated through isotopic labeling. Insights into mechanism transformation well substrate scope this selective reaction described, essential phenylsilane PBIT disclosed. Among several relevant species characterized an unprecedented Co(III) complex dianionic diradical ligand ([CoIII(LSMe••)I]).

Язык: Английский

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Efficient hydrogenation of CO₂ to formic acid in water without consumption of a base

Green Chemistry, Год журнала: 2022, Номер 24(17), С. 6727 - 6732

Опубликована: Янв. 1, 2022

CO 2 hydrogenation to formic acid was achieved without consumption of a base and turnover number up 364 249 obtained. HCOOH is isolatable the catalyst–base system easily recycled.

Язык: Английский

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An Adaptive Rhodium Catalyst to Control the Hydrogenation Network of Nitroarenes

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(36)

Опубликована: Июнь 27, 2022

An adaptive catalytic system that provides control over the nitroarene hydrogenation network to prepare a wide range of aniline and hydroxylamine derivatives is presented. This takes advantage delicate interplay between rhodium(III) center Lewis acidic borane introduced in secondary coordination sphere metal. The high chemoselectivity catalyst presence various potentially vulnerable functional groups its readiness be deployed at preparative scale illustrate practicality. Mechanistic studies density theory (DFT) methods were used shed light on mode functioning elucidate origin adaptivity. competition for interaction with boron solvent molecule substrate was found crucial When operating THF, reduction stops platform, whereas reaction can directed platform toluene.

Язык: Английский

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Selective Reduction of CO₂ to Methanol via Hydrosilylation Boosted by a Porphyrinic Metal–Organic Framework

ACS Catalysis, Год журнала: 2023, Номер 13(10), С. 6837 - 6845

Опубликована: Май 4, 2023

Methanol has been widely used in organic synthesis and fuel fields. The capture selective reduction of CO2 to methanol can not only decrease concentrations but also produce as a value-added chemical fuel. Herein, the via hydrosilylation was reported be accelerated by porphyrinic metal–organic framework (Ir-PCN-222). Catalytic results showed that Ir-PCN-222 efficient for reduction. Under atmospheric pressure, turnover frequency up 157 h–1 number could reach 1875 with catalyst. catalytic reactions accomplished under low concentration (15% 85% N2) more than 99% conversion selectivity. reaction mechanism studied density functional theory calculations molecular dynamics simulations, revealing balance between hydrosilanes around catalytically active iridium porphyrin units confined spaces played an important role product

Язык: Английский

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Theory-guided development of homogeneous catalysts for the reduction of CO₂to formate, formaldehyde, and methanol derivatives

Chemical Science, Год журнала: 2023, Номер 14(11), С. 2799 - 2807

Опубликована: Янв. 1, 2023

Computational volcano plots are used to predict selectivity in the context of (first-row) transition metal-catalyzed CO 2 reduction. The expected trends were tested experimentally and allowed for systematic improvement catalyst.

Язык: Английский

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Co‐catalyzed Selective syn‐Hydrosilylation of Internal Alkynes

ChemCatChem, Год журнала: 2023, Номер 15(14)

Опубликована: Май 30, 2023

Abstract Vinylsilanes are highly appealing and convenient chemical derivatives, as evidenced by the increasing number of synthetic transformations utilizing this class compounds. Herein, a new comprehensive cobalt‐catalyzed procedure has been developed enabling selective hydrosilylation internal aryl‐, alkyl‐, silylalkynes. Cobalt complexes bearing triazine‐based PNP pincer‐type ligands provide exclusive syn ‐addition primary well secondary silanes to C≡C bonds. As result, ( E )‐silylalkenes vicinal disilylalkenes were effectively obtained with excellent stereoselectivity regioselectivity. Unlike several TM‐catalyzed procedures, no external additives required since hydrosilanes act both substrates activators.

Язык: Английский

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Cobalt-catalyzed dehydrogenative cross-coupling reaction: Selective access to dihydrosiloxanes, hydrosiloxanes and functionalized silsesquioxanes

Journal of Catalysis, Год журнала: 2023, Номер 423, С. 1 - 9

Опубликована: Апрель 27, 2023

Disclosed is a mild, scalable, and chemoselective cross-dehydrogenative functionalization protocol for the construction of Si−O−Si moieties under cobalt catalysis. The reaction has broad scope can be used to synthesize wide range silicon building blocks, including challenging dihydrosiloxanes functionalized silsesquioxanes. Most importantly, results are placed into context by benchmarking with state-of-the-art methods. Remarkably, utilized PNP-Co catalyst enables development further synthetic strategies such as one-pot sequential silanolysis/alcoholysis process or unprecedented dehydrocoupling between germanol hydrosilane.

Язык: Английский

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