Dinitrogen complexation and reduction at low-valent calcium

Science, Journal Year: 2021, Volume and Issue: 371(6534), P. 1125 - 1128

Published: March 11, 2021

Calcium catches dinitrogen Although lithium reduces dinitrogen, the other alkali and alkaline Earth metals have proven largely inert to gas under ambient conditions. Rösch et al. report that with just right β-diketiminate ligand an assist from potassium as terminal reductant, calcium can mediate reduction. Crystallography spectroscopic characterization revealed a product in which doubly reduced adopted side-on bridging motif between two centers. A subsequent reaction coordinated tetrahydrofuran appeared release diazene. Science , this issue p. 1125

Language: Английский

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Nitrogen Fixation via Splitting into Nitrido Complexes

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(11), P. 6522 - 6587

Published: May 11, 2021

The large carbon footprint of the Haber–Bosch process, which provides ammonia for fertilizers but also feedstock all nitrogenous commercial products, has fueled quest alternative synthetic strategies to nitrogen fixation. Owing extraordinarily strong N≡N triple bond, key step reaction, i.e., dissociative adsorption N2, requires high temperatures. Since first report in 1995, a wide variety molecular transition metal and f-block compounds have been reported that can fully cleave N2 at ambient conditions form well-defined nitrido complexes. We here provide comprehensive survey current state splitting reactions solution follow-up transfer reactivity. Particular emphasis is put on electronic structure requirements formation suitable precursors their N–N scission prospects synthesis containing products will be discussed, ranging from heterocumulenes organic amines, amides or nitriles via proton coupled electron transfer, carbonylation, electrophilic functionalization derived Accomplishments challenges fixation are presented offer guidelines development catalytic platforms.

Language: Английский

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Direct transformation of dinitrogen: synthesis of N-containing organic compounds via N−C bond formation

National Science Review, Journal Year: 2020, Volume and Issue: 7(10), P. 1564 - 1583

Published: June 23, 2020

Abstract N-containing organic compounds are of vital importance to lives. Practical synthesis valuable directly from dinitrogen (N2), not through ammonia (NH3), is a holy-grail in chemistry and chemical industry. An essential step for this transformation the functionalization activated N2 units/ligands generate N−C bonds. Pioneering works transition metal-mediated direct conversion into via bond formation at metal-dinitrogen [N2-M] complexes have generated diversified coordination modes laid foundation understanding mechanism. This review summarizes those major achievements organized by (end-on, side-on, end-on-side-on, etc.) that involved steps, each part arranged terms reaction types (N-alkylation, N-acylation, cycloaddition, insertion, between carbon-based substrates. Additionally, earlier on one-pot ill-defined intermediates also briefed. Although almost all syntheses so far literature realized homogeneous stoichiometric thermochemical systems discussed here detail, sporadically reported involving photochemical, electrochemical, heterogeneous thermo-catalytic reactions, if any, mentioned. aims provide readers with an in-depth state-of-the-art perspectives future research particularly catalytic efficient under mild conditions, stimulate more efforts tackle long-standing grand scientific challenge.

Language: Английский

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Comprehensive insights into synthetic nitrogen fixation assisted by molecular catalysts under ambient or mild conditions

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(8), P. 5201 - 5242

Published: Jan. 1, 2021

N₂is fixed as NH₃industrially by the Haber–Bosch process under harsh conditions, whereas biological nitrogen fixation is achieved ambient which has prompted development of alternative methods to fix N₂catalyzed transition metal molecular complexes.

Language: Английский

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Conceptual and Practical Aspects of Metal–Organic Frameworks for Solid–Gas Reactions

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(9), P. 6197 - 6232

Published: Feb. 17, 2023

The presence of site-isolated and well-defined metal sites has enabled the use metal–organic frameworks (MOFs) as catalysts that can be rationally modulated. Because MOFs addressed manipulated through molecular synthetic pathways, they are chemically similar to catalysts. They are, nevertheless, solid-state materials therefore thought privileged solid excel in applications involving gas-phase reactions. This contrasts with homogeneous catalysts, which overwhelmingly used solution phase. Herein, we review theories dictating gas phase reactivity within porous solids discuss key catalytic gas–solid We further treat theoretical aspects diffusion confined pores, enrichment adsorbates, types solvation spheres a MOF might impart on definitions acidity/basicity absence solvent, stabilization reactive intermediates, generation characterization defect sites. reactions broadly include reductive (olefin hydrogenation, semihydrogenation, selective reduction), oxidative (oxygenation hydrocarbons, dehydrogenation, carbon monoxide oxidation), C–C bond forming dimerization/polymerization, isomerization, carbonylation reactions).

Language: Английский

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Low oxidation state and hydrido group 2 complexes: synthesis and applications in the activation of gaseous substrates

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(10), P. 5054 - 5082

Published: Jan. 1, 2024

This review summarises advances in the chemistry of low-oxidation state and hydrido group 2 metal complexes, focussing on their use for reductive activation feed-stock gaseous small molecules, subsequent transformation into value added products.

Language: Английский

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Construction of N−E bonds via Lewis acid-promoted functionalization of chromium-dinitrogen complexes

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 15, 2025

Language: Английский

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Diverse Behaviors of N₂ on Mo Centers Bearing POCOP-Pincer Ligands and the Role of π-Electron Configuration in Regulating the Pathway of N₂ Activation

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

Activation of N2 through transition-metal complexes has emerged as a powerful strategy for fixation under mild conditions. Dissociative route and associative are considered two major routes transformation on complexes. Homolysis between metal fragments is the crucial step dissociative been proven to be an efficient approach terminal nitride, which key intermediate both routes. Hence, conditions cleavage have attracted much interest discussion. Herein, we investigated reactivity when coordinated Mo centers bearing POCOP-pincer ligands isolated characterized many novel N2-related intermediates such [(POCOPCy)MoI]2(μ-N2) (2Cy), (POCOPCy)Mo(N)(μ-N)MoI (5Cy), {[(POCOPCy)Mo(N2)2]2(μ-N2)}[Na(crypt-222)] (6Cy-crypt), [(POCOPCy)Mo(N2)2(μ-N2)Mo(N)]Na (8Cy). The influences oxidation state centers, π electrons, reaction conditions, etc., N2-reactivity were also studied experimentally theoretically. Accordingly, some fundamental understanding regulation activation pathways was proposed: N2-bridged dimer without ligand trans bridging preferred structure cleavage; having adequate electrons transferred into σ–σ*−σ related orbital in {MoNNMo} manifold key; heating or electron excitation advantageous route.

Language: Английский

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Coupling dinitrogen and hydrocarbons through aryl migration

Nature, Journal Year: 2020, Volume and Issue: 584(7820), P. 221 - 226

Published: Aug. 12, 2020

Language: Английский

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Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 27(12), P. 3892 - 3928

Published: Sept. 28, 2020

Dinitrogen (N

Language: Английский

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