Carbon Dioxide Hydrogenation to Formate Catalyzed by a Bench-Stable, Non-Pincer-Type Mn(I) Alkylcarbonyl Complex DOI Creative Commons
Sylwia Kostera, Stefan Weber, Maurizio Peruzzini

et al.

Organometallics, Journal Year: 2021, Volume and Issue: 40(9), P. 1213 - 1220

Published: April 20, 2021

The catalytic reduction of carbon dioxide is a process growing interest for the use this simple and abundant molecule as renewable building block in C1-chemical synthesis hydrogen storage. well-defined, bench-stable alkylcarbonyl Mn(I) bis(phosphine) complex fac-[Mn(CH2CH2CH3)(dippe)(CO)3] [dippe = 1,2-bis(diisopropylphosphino)ethane] was tested an efficient selective non-precious-metal precatalyst hydrogenation CO2 to formate under mild conditions (75 bar total pressure, 80 °C), presence Lewis acid co-catalyst (LiOTf) base (DBU). Mechanistic insight into reaction provided by means density functional theory (DFT) calculations.

Language: Английский

Catalytic methods for chemical recycling or upcycling of commercial polymers DOI
Sophia C. Kosloski-Oh, Zachary A. Wood, Yvonne Manjarrez

et al.

Materials Horizons, Journal Year: 2020, Volume and Issue: 8(4), P. 1084 - 1129

Published: Dec. 23, 2020

A review covering catalytic method development to enable efficient chemical recycling and upcycling of the most abundant commercial polymers.

Language: Английский

Citations

282

Homogeneous and heterogeneous catalysts for hydrogenation of CO2 to methanol under mild conditions DOI

Shao‐Tao Bai,

Gilles De Smet, Yuhe Liao

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(7), P. 4259 - 4298

Published: Jan. 1, 2021

This review summarizes the concepts, mechanisms, drawbacks and challenges of state-of-the-art catalysis for CO2 to MeOH under mild conditions. Thoughtful guidelines principles future research are presented discussed.

Language: Английский

Citations

253

Homogeneous manganese-catalyzed hydrogenation and dehydrogenation reactions DOI Creative Commons
Yujie Wang, Mingyang Wang, Yibiao Li

et al.

Chem, Journal Year: 2020, Volume and Issue: 7(5), P. 1180 - 1223

Published: Dec. 9, 2020

Language: Английский

Citations

218

Lutidine‐Based Chiral Pincer Manganese Catalysts for Enantioselective Hydrogenation of Ketones DOI
Linli Zhang,

Yitian Tang,

Zhaobin Han

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(15), P. 4973 - 4977

Published: Feb. 18, 2019

A series of MnI complexes containing lutidine-based chiral pincer ligands with modular and tunable structures has been developed. The complex shows unprecedentedly high activities (up to 9800 TON; TON=turnover number), broad substrate scope (81 examples), good functional-group tolerance, excellent enantioselectivities (85-98 % ee) in the hydrogenation various ketones. These aspects are rare earth-abundant metal catalyzed hydrogenations. utility protocol have demonstrated asymmetric synthesis a variety key intermediates for drugs. Preliminary mechanistic investigations indicate that an outer-sphere mode substrate-catalyst interactions probably dominates catalysis.

Language: Английский

Citations

192

Hydrogenative Depolymerization of Nylons DOI Creative Commons
Amit Kumar, Niklas von Wolff,

Michael Rauch

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(33), P. 14267 - 14275

Published: July 24, 2020

The widespread crisis of plastic pollution demands discovery new and sustainable approaches to degrade robust plastics such as nylons. Using a green approach based on hydrogenation, in the presence ruthenium pincer catalyst at 150 °C 70 bar H2, we report here first example hydrogenative depolymerization conventional, widely used nylons polyamides, general. Under same catalytic conditions, also demonstrate hydrogenation polyurethane produce diol, diamine, methanol. Additionally, an where monomers (and oligomers) obtained from process can be dehydrogenated back poly(oligo)amide approximately similar molecular weight, thus completing closed loop cycle for recycling polyamides. Based experimental density functional theory studies, propose that is facilitated by metal–ligand cooperativity. Overall, this unprecedented transformation, albeit proof concept level, offers toward cleaner route

Language: Английский

Citations

162

Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions DOI
Kuhali Das, Satyadeep Waiba, Akash Jana

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(11), P. 4386 - 4464

Published: Jan. 1, 2022

The emerging field of organometallic catalysis has shifted towards research on Earth-abundant transition metals due to their ready availability, economic advantage, and novel properties. In this case, manganese, the third most abundant transition-metal in Earth's crust, emerged as one leading competitors. Accordingly, a large number molecularly-defined Mn-complexes been synthesized employed for hydrogenation, dehydrogenation, hydroelementation reactions. regard, catalyst design is based three pillars, namely, metal-ligand bifunctionality, ligand hemilability, redox activity. Indeed, developed catalysts not only differ chelating atoms they possess but also working principles, thereby different turnover numbers product molecules. Hence, critical assessment molecularly defined manganese terms atoms, reaction conditions, mechanistic pathway, significant. Herein, we analyze complexes catalytic activity, versatility allow multiple transformations routes convert substrates target This article will be helpful get significant insight into design, aiding design.

Language: Английский

Citations

160

Development of a practical non-noble metal catalyst for hydrogenation of N-heteroarenes DOI
Veronica Papa, Yi-Xuan Cao,

Anke Spannenberg

et al.

Nature Catalysis, Journal Year: 2020, Volume and Issue: 3(2), P. 135 - 142

Published: Jan. 6, 2020

Language: Английский

Citations

156

Robust and efficient hydrogenation of carbonyl compounds catalysed by mixed donor Mn(I) pincer complexes DOI Creative Commons
Wenjun Yang, Ivan Yu. Chernyshov, Robin K. A. van Schendel

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Jan. 4, 2021

Abstract Any catalyst should be efficient and stable to implemented in practice. This requirement is particularly valid for manganese hydrogenation catalysts. While representing a more sustainable alternative conventional noble metal-based systems, catalysts are prone degrade under catalytic conditions once operation temperatures high. Herein, we report highly Mn(I)-CNP pre-catalyst which gives rise the excellent productivity (TOF° up 41 000 h −1 ) stability (TON 200 000) catalysis. system enables near-quantitative of ketones, imines, aldehydes formate esters at loadings as low 5–200 p.p.m. Our analysis points crucial role activation step performance system. employing alkoxide bases can ultimately provide catalytically competent species hydrogen atmosphere, Mn(I) with hydride donor promoters, e.g. KHBEt 3 , dramatically improves eliminates induction times associated slow activation.

Language: Английский

Citations

152

Homogeneous Hydrogenation of CO2 and CO to Methanol: The Renaissance of Low‐Temperature Catalysis in the Context of the Methanol Economy DOI Creative Commons
Raktim Sen, Alain Goeppert, G. K. Surya Prakash

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(42)

Published: Aug. 3, 2022

The traditional economy based on carbon-intensive fuels and materials has led to an exponential rise in anthropogenic CO

Language: Английский

Citations

73

Metal-catalyzed plastic depolymerization DOI Creative Commons
Kishor V. Khopade, Samir H. Chikkali, Nagaraju Barsu

et al.

Cell Reports Physical Science, Journal Year: 2023, Volume and Issue: 4(5), P. 101341 - 101341

Published: March 29, 2023

Polymers have become an indispensable part of our daily lives, and today we produce around 370 MT plastic per year. Only about 20% it is being recycled, the rest, 80%, unleashed into environment without appropriate treatment. This calls forth evaluation strategies available for mitigating menace "after-use" waste. Various approaches evolved over a decade are at different levels development. Plastic depolymerization upcycling considered some most prominent long-term solutions. The metal-catalyzed waste to chemical feedstocks has emerged as one promising ways address global pollution. Therefore, this review aims examine methods, notify recent progress, pinpoint current gaps, gauge potential strategy. Both homogeneous heterogeneous catalysts been reported depolymerize various polymers last decade. Considerable advances in metal-mediated polyolefins, polyesters, polycarbonates, polyurethanes, polyamides, polyethers. above produces monomers or intermediates, which can be used again polymerization thus brings back circularity. overview debates usage high temperatures, sophisticated ligands, expensive metals, stoichiometric reagents, etc., depolymerization. Thus, summarizes understanding fundamental science depolymerization, remaining scientific challenges, opportunities.

Language: Английский

Citations

46