First-Row Transition Metal (De)Hydrogenation Catalysis Based On Functional Pincer Ligands

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2681 - 2751

Published: Dec. 31, 2018

The use of 3d metals in de/hydrogenation catalysis has emerged as a competitive field with respect to "traditional" precious metal catalyzed transformations. introduction functional pincer ligands that can store protons and/or electrons expressed by metal-ligand cooperativity and ligand redox-activity strongly stimulated this development conceptual starting point for rational catalyst design. This review aims at providing comprehensive picture the utilization first-row transition hydrogenation dehydrogenation related synthetic concepts relying on these such hydrogen borrowing methodology. Particular emphasis is put implementation relevance cooperating redox-active within mechanistic scenarios.

Language: Английский

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3d-Metal Catalyzed N- and C-Alkylation Reactions via Borrowing Hydrogen or Hydrogen Autotransfer

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2524 - 2549

Published: Nov. 20, 2018

The conservation of our element resources is a fundamental challenge mankind. development alcohol refunctionalization reactions possible fossil carbon strategy since alcohols can be obtained from indigestible and abundantly available biomass. rare noble metals, frequently used in key technologies such as catalysis, might feasible by replacing them with highly abundant metals. alkylation amines related C–C coupling are early examples reactions. These follow mostly the borrowing hydrogen or autotransfer catalysis concept, many 3d-metal catalysts have been disclosed recent years. In this review, we summarize progress made developing Cu, Ni, Co, Fe, Mn for C–N bond formation using concept. We expect that findings field will inspire others to develop new efficient selective earth-abundant metal applications novel mediated

Language: Английский

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Catalytic (de)hydrogenation promoted by non-precious metals – Co, Fe and Mn: recent advances in an emerging field

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(4), P. 1459 - 1483

Published: Jan. 1, 2018

Catalytic hydrogenation and dehydrogenation reactions form the core of modern chemical industry. This vast class is found in any part synthesis starting from milligram-scale exploratory organic chemistry to multi-ton base chemicals production. Noble metal catalysis has long been key driving force enabling these transformations with carbonyl substrates their nitrogen-containing counterparts. review aimed at introducing reader remarkable progress made last three years development catalysts for hydrogenations dehydrogenative transformations.

Language: Английский

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Manganese Complexes for (De)Hydrogenation Catalysis: A Comparison to Cobalt and Iron Catalysts

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 57(1), P. 46 - 60

Published: Oct. 24, 2017

The sustainable use of the resources on our planet is essential. Noble metals are very rare and diversely used in key technologies, such as catalysis. Manganese third most abundant transition metal Earth's crust based recently discovered impressive reactivity hydrogenation dehydrogenation reactions, a potentially useful noble-metal "replacement". hope novel selectivity profiles, not possible with noble metals, also an aim manganese complexes (de)hydrogenation reactions was demonstrated for first time 2016. Herein, we summarize work that has been published since then especially discuss importance homogeneous catalysts comparison to cobalt iron catalysts.

Language: Английский

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Homogeneous Catalysis by Cobalt and Manganese Pincer Complexes

ACS Catalysis, Journal Year: 2018, Volume and Issue: 8(12), P. 11435 - 11469

Published: Oct. 16, 2018

Homogeneous catalysis of organic transformations by metal complexes has been mostly based on noble metals. In recent years, tremendous progress made in the field base-metal catalysis, with pincer-type complexes, such as iron, cobalt, nickel, and manganese pincer systems. Particularly impressive is explosive growth Mn-based first being reported recently 2016. This review covers homogeneously catalyzed reactions using cobalt manganese. Various are described, including acceptorless dehydrogenation, hydrogenation, dehydrogenative coupling, hydrogen borrowing, transfer, H–X additions, C–C alkene polymerization N2 fixation, their scope brief mechanistic comments.

Language: Английский

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Homogeneous Catalysis for Sustainable Energy: Hydrogen and Methanol Economies, Fuels from Biomass, and Related Topics

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(1), P. 385 - 441

Published: Nov. 2, 2021

As the world pledges to significantly cut carbon emissions, demand for sustainable and clean energy has now become more important than ever. This includes both production storage of carriers, a majority which involve catalytic reactions. article reviews recent developments homogeneous catalysts in emerging applications energy. The most focus been on hydrogen as several efficient have reported recently (de)hydrogenative transformations promising economy. Another direction that extensively covered this review is methanol Homogeneous investigated from CO

Language: Английский

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Recent advances in homogeneous borrowing hydrogen catalysis using earth-abundant first row transition metals

Organic & Biomolecular Chemistry, Journal Year: 2018, Volume and Issue: 17(7), P. 1595 - 1607

Published: Sept. 17, 2018

The review highlights the recent advances (2013-present) in use of earth-abundant first row transition metals homogeneous borrowing hydrogen catalysis. utility catalysts based on Mn, Fe, Co, Ni and Cu to promote a diverse array important C-C C-N bond forming reactions is described, including discussion reaction mechanisms, scope limitations, future challenges this burgeoning area sustainable

Language: Английский

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Borrowing Hydrogen for Organic Synthesis

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(4), P. 570 - 585

Published: March 25, 2021

Borrowing hydrogen is a process that used to diversify the synthetic utility of commodity alcohols. A catalyst first oxidizes an alcohol by removing form reactive carbonyl compound. This intermediate can undergo diverse range subsequent transformations before returns "borrowed" liberate product and regenerate catalyst. In this way, alcohols may be as alkylating agents whereby sole byproduct one-pot reaction water. recent decades, significant advances have been made in area, demonstrating many effective methods access valuable products. outlook highlights diversity metal biocatalysts are available for approach, well various performed, focusing on selection most advances. By succinctly describing conveying versatility borrowing chemistry, we anticipate its uptake will increase across wider scientific audience, expanding opportunities further development.

Language: Английский

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Isoelectronic Manganese and Iron Hydrogenation/Dehydrogenation Catalysts: Similarities and Divergences

Accounts of Chemical Research, Journal Year: 2018, Volume and Issue: 51(6), P. 1558 - 1569

Published: June 4, 2018

ConspectusSustainable processes that utilize nontoxic, readily available, and inexpensive starting materials for organic synthesis constitute a major objective in modern chemical research. In this context, it is highly important to perform reactions under catalytic conditions replace precious metal catalysts by earth-abundant nonprecious catalysts. particular, iron manganese are promising candidates, as these among the most abundant metals earth's crust, inexpensive, exhibit low environmental impact. As far concerned, hydrogenations acceptorless alcohol dehydrogenation (AAD), sometimes conjunction with hydrogen autotransfer reactions, becoming areas of While first very synthetic process representing atom-efficient clean methodology, AAD an oxidant-free, environmentally benign reaction where carbonyl compounds together dihydrogen valuable product and/or reactant (autotransfer) water formed. Carbonyl compounds, typically generated situ, can be converted into other useful such amines, imines, or heterocycles.In 2016 several groups, including ours, discovered time potential hydride biscarbonyl Mn(I) complexes bearing strongly bound PNP pincer ligands related tridentate effective versatile hydrogenation, transfer reactions. These isoelectronic analogues respective monocarbonyl Fe(II) display similar reactivities but also quite divergent behavior depending on coligands. Moreover, show improved long-term stability high robustness toward harsh conditions. light recent achievements, Account contrasts catalysts, highlighting specific features connected particular structural electronic properties. It addresses opportunities restrictions their applications. Apart from classical hydrogenations, covers developments resulting complex molecules heterocycles via multicomponent The ambivalent hydrogen-based redox chemistry provides access variety synthetically reductive oxidative coupling Hence, cover broad scope applications activities productivities competitive those well-established knowledge about nature characteristics active Mn(I)- Fe(II)-based systems paves way conceptually mechanistically well-founded research, which might lead further discovery novel extending current limitations reactivity. underlines base beginning challenge contributes advancement waste-free sustainable catalysis.

Language: Английский

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Strategies and mechanisms of metal–ligand cooperativity in first-row transition metal complex catalysts

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(24), P. 8933 - 8987

Published: Jan. 1, 2020

The use of metal–ligand cooperation (MLC) by transition metal bifunctional catalysts has emerged at the forefront homogeneous catalysis science.

Language: Английский

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